WO1989008608A1 - Synthetic crystalline molecular sieve and its synthesis - Google Patents
Synthetic crystalline molecular sieve and its synthesis Download PDFInfo
- Publication number
- WO1989008608A1 WO1989008608A1 PCT/US1989/000824 US8900824W WO8908608A1 WO 1989008608 A1 WO1989008608 A1 WO 1989008608A1 US 8900824 W US8900824 W US 8900824W WO 8908608 A1 WO8908608 A1 WO 8908608A1
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- WIPO (PCT)
- Prior art keywords
- molecular sieve
- composition
- valence
- silicon
- crystalline
- Prior art date
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 20
- 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 abstract description 20
- 230000015572 biosynthetic process Effects 0.000 title description 6
- 238000003786 synthesis reaction Methods 0.000 title description 6
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000011541 reaction mixture Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 49
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 43
- 239000013078 crystal Substances 0.000 claims description 21
- 229910052593 corundum Inorganic materials 0.000 claims description 17
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical group NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001768 cations Chemical group 0.000 claims description 9
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical group NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 150000001450 anions Chemical group 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 239000010457 zeolite Substances 0.000 description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910021536 Zeolite Inorganic materials 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- -1 alkaline earth metal cation Chemical class 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 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 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000002178 crystalline material Substances 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical group O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 125000004429 atom Chemical group 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
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 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
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 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
- 229910001649 dickite Inorganic materials 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IZKZIDXHCDIZKY-UHFFFAOYSA-N heptane-1,1-diamine Chemical compound CCCCCCC(N)N IZKZIDXHCDIZKY-UHFFFAOYSA-N 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052744 lithium 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 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
- 230000010287 polarization Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012429 reaction media Substances 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
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-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
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
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
-
- 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
- B01J29/85—Silicoaluminophosphates [SAPO 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
Definitions
- This invention relates to a synthetic crystalline molecular sieve and to a method of its synthesis.
- Zeolitic materials both natural and synthetic, have been demonstrated in the past to have catalytic properties for various types of hydrocarbon conversion.
- Certain zeolitic materials are ordered, porous crystalline aluminosilicates having a definite crystalline structure as determined by X-ray diffraction, within which there are a large number of smaller cavities which may be interconnected by a number of still smaller channels or pores. These cavities and pores are uniform in size within a specific zeolitic material. Since the dimensions of these pores are such as to accept for adsorption molecules of certain dimensions while rejecting those of larger dimensions, these materials have come to be known as "molecular sieves" and are utilized in a variety of ways to take advantage of these properties.
- Such molecular sieves include a wide variety of positive ion-containing crystalline aluminosilicates.
- These aluminosilicates can be described as rigid three-dimensional frameworks of SiO 4 and AlO 4 in which the tetrahedra are cross-linked by the sharing of oxygen atoms whereby the ratio of the total aluminum and silicon atoms to oxygen atoms is 1:2.
- the electrovalence of the tetrahedra containing aluminum is balanced by the inclusion in the crystal of a cation, for example an alkali metal or an alkaline earth metal cation. This can be expressed wherein the ratio of aluminum to the number of various cations, such as Ca/2, Sr/2, Na, K or Li, is equal to unity.
- One type of cation may be exchanged either entirely or partially with another type of cation utilizing ion exchange techniques in a conventional manner.
- cation exchange it has been possible to vary the properties of a given aluminosilicate by suitable selection of the cation.
- Prior art techniques have resulted in the formation of a great variety of synthetic zeolites.
- the zeolites have come to be designated by letter or other convenient symbols, as illustrated by zeolite A (U.S. Patent 2,882,243), zeolite X (U.S. Patent 2,882,244), zeolite Y (U.S. Patent 3,130,007), zeolite ZK-5 (U.S.
- Patent 3,247,195 zeolite ZK-4 (U.S. Patent 3,314,752), zeolite ZSM-5 (U.S. Patent 3,702,886), zeolite ZSM-11 (U.S. Patent 3,709,979), zeolite ZSM-12 (U.S. Patent 3,832,449), zeolite ZSM-20 (U.S. Patent 3,972,983), zeolite ZSM-35 (U.S. Patent 4,016,245), and zeolite ZSM-23 (U.S. Patent 4,076,842).
- Aluminum phosphates are taught in, for example, U.S.
- U.S. Patent 3,801,704 teaches an aluminum phosphate treated in a certain way to impart acuity.
- Microporous aluminum phosphates have a composition typified as:
- R is an organic amine or quaternary ammonium salt entrapped within the aluminum phosphate and playing a role as crystallization template, x and y representing the amounts of R and H 2 O needed to fill the microporous voids. Because the aluminum/phosphorus atomic ratio of these materials is about unity, they display virtually no ion-exchange properties, the framework positive charge on phosphorus being balanced by corresponding negative charge on aluminum:
- AlPO 4 (AlO 2 -)(PO 2 + )
- Silicoaluminophosphates having a variety of structures have also been synthesized, see, for example, Nosa 4,440,871, 4,623,527, 4,639,358, 4,647,442, 4,664,897, 4,639,357 and 4,632,811. Crystalline metalloaluminophosphates are disclosed in U.S. Patent No.4, 713, 227, an antimonophosphoaluminate is disclosed in U.S.
- Patent No.4,619, 818 and a titaniumaluminophosphate is disclosed in U.S. Patent No. 4,500,651.
- the present invention resides in a synthetic crystalline molecular sieve having the following x-ray diffraction lines:
- the interplanar spacings, d's were calculated in Angstrom units d(A) and the relative intensities of the lines, I/I o , where I o 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.
- the metalloaluminophosphate When z is greater than 0, the metalloaluminophosphate will mostly behave as a cation exchanger with potential use as an acidic catalyst. When z is less than 0, the metalloaluminophosphate will mostly behave as an anion exchanger with potential use as a basic catalyst.
- the element M is silicon alone and the molecular sieve has the following composition: where 0.01 ⁇ x ⁇ 1
- the element M includes an element other than silicon having an oxidation number of +2 to +6 and an ionic "Radius Ratio" of 0.15 to 0.73 , with the proviso that , when the oxidation number is +2, the Radius Ratio must be 0.52 to 0.62.
- silicon may also be present such that the ratio silicon:non-silicon atoms in the MO 2 component is less than 1, preferably less than 0.5.
- Ratius Ratio is defined as the ratio of the crystal ionic radius of the element M to the crystal ionic radius of the oxygen anion, 0 -2 .
- Non-limiting examples of element M useful herein include:
- Non-limiting example of elements not included as M of the present invention include:
- the crystalline composition comprises structural aluminum, phosphorus and element M, and will exhibit an M/(aluminum plus phosphorus) atomic ratio of less than unity and greater than zero, and usually within the range of from 0.001 to 0.99.
- the phosphorus/aluminum atomic ratio of such materials may be found to vary from 0.01 to 100.0 , as synthesized. It is well recognized that aluminum phosphates exhibit a phosphorus/aluminum atomic ratio of unity, and essentially no element M.
- the phosphorus-substituted zeolite compositions sometimes referred to as "aluminosilicophosphate" zeolites, have a silicon/aluminum atomic ratio of usually greater than unity, and generally from 0.66 to 8.0, and a phosphorus/aluminum atomic ratio of less than unity, and usually from 0 to 1.
- the molecular sieve of the invention is prepared from a reaction mixture hydrogel containing sources of oxides of aluminum , phosphorus and the non-aluminum, non-phosphorus element M, a directing agent R, and water and having a composition , in terms of mole ratios , within the following ranges:
- R is a C 5 - C 7 alkyldiamine, such as , for example, pentanediamine, e .g . 1 ,5-pentanediamine and heptanediamine, e.g . 1 ,7-heptanediamine.
- Suitable reaction conditions include a temperature of 80°C to 300°C for a period of time from 5 hours to 20 days. A more preferred temperature range is from 100°C to 200°C with a crystallization time of 24 hours to 10 days.
- the reaction of the gel particles is carried out until crystals form.
- the solid product comprising the desired metalloaluminophosphate is then recovered from the reaction medium, such as by cooling the whole to room temperature , filtering and water washing .
- the synthesis may be facilitated when the reaction mixture comprises seed crystals , such as those having the structure of the product crystals .
- seed crystals such as those having the structure of the product crystals .
- the use of at least 0.01%, preferably about 0.10% , and even more preferably about 1% seed crystals (based on total weight) of crystalline material in the reaction mixture will facilitate crystallization in the present method.
- the organic directing agent used in the synthesis of the molecular sieve of the invention can be removed to allow access to its internal pore structure by calcining in conventional manner , e.g. at 200 - 550°C for 1 - 48 hours .
- the improved crystalline composition of the present invention may be used as a catalyst component in a wide variety of organic compound, e.g. hydrocarbon compound, conversion reactions, it is notably useful in the processes of cracking, hydrocracking, isomerization and reforming.
- Other conversion processes for which the present composition may be utilized as a catalyst component include, for example, dewaxing.
- the crystalline metalloaluminophosphate composition prepared in accordance herewith can be used either in the as-synthesized form, the hydrogen form or another univalent or multivalent cationic form. It can also be used in intimate combination with a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed. Such components can be exchanged into the composition, impregnated therein or physically intimately admixed therewith.
- Such components can be impregnated in or on to the crystalline composition such as, for example, by, in the case of platinum, treating the material with a platinum metal-containing ion.
- Suitable platinum compounds for this purpose include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex. Combinations of metals and methods for their introduction can also be used.
- the present composition when employed either as an adsorbent or as a catalyst in a hydrocarbon conversion process, should be dehydrated at least partially. This can be done by heating to a temperature in the range of 65°C to 315°C in an inert atmosphere, such as air or nitrogen, and at atmospheric or subatmospheric pressures for between 1 and 48 hours.
- Dehydration can be performed at lower temperature merely by placing the zeolite in a vacuum, but a longer time is required to obtain a particular degree of dehydration.
- matrix materials include active and inactive materials and synthetic or naturally occurring zeolites as well as incorganic materials such as clays, silica and/or metal oxides, e.g. alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates, sols or gels including mixtures of silica and metal oxides.
- Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate or reaction.
- crystalline catalytic materials have been incorporated into naturally occurring clays, e.g. bentonite and kaolin. These materials, i.e. clays, oxides, etc., function, in part, as binders for the catalyst. It is desirable to provide a catalyst having good crush strength, because in a petroleum refinery the catalyst is often subjected to rough handling, which tends to break the catalyst down into powder-like materials which cause problems in processing.
- Naturally occurring clays which can be composited with the hereby synthesized metalloaluminophosphate include the montmorillonite and kaolin families which include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays, or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
- the crystals hereby synthesized can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, s ⁇ lica-beryllia , silica-titania , as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.
- the matrix can be in the form of a cogel . A mixture of these components could also be used .
- the relative proportions of finely divided crystalline material and matrix vary widely with the crystalline material content ranging from 1 to 90 percent by weight, and more usually in the range of 2 to 50 percent by weight of the composite.
- Reforming stocks can be reformed employing a temperature between 450°C and 550°C.
- the pressure can be between 445 and 3550 kPa (50 and 500 psig), but is preferably between 890 and 2170 kPa (100 and 300 psig).
- the liquid hourly space velocity is generally between 0.1 and 10 hr -1 , preferably between 1 and 4 hr -1 and the hydrogen to hydrocarbon mole ratio is generally between 1 and 10, preferably between 3 and 5.
- a catalyst comprising the present composition can also be used for hydroisomerization of normal parrffins, when provided with a hydrogenation component, e.g. platinum. Hydroisomerization is carried out at a temperature between 250°C to 450°C, preferably 300°C to 425°C, with a liquid hourly space velocity between 0.1 and 10 hr -1 , preferably between 0.5 and 4 hr -1 , employing hydrogen such that the hydrogen to hydrocarbon mole ratio is between 1 and 10. Additionally, the catalyst can be used for olefin or aromatics isomerization employing temperatures between 0°C and 550°C.
- a catalyst comprising the metalloaluminophosphate of this invention can also be used for reducing the pour point of gas oils. This process is carried out at a liquid hourly space velocity between 0.1 and 5 hr -1 and a temperature between 300°C and 425°C.
- a catalyst comprising the composition of this invention containing a metal, e.g. platinum
- a metal e.g. platinum
- hydrogenation-dehydrogenation reactions and desulfurization reactions include hydrogenation-dehydrogenation reactions and desulfurization reactions , olefin polymerization (oligomerization) , and other organic compound conversions such as the conversion of alcohols (e.g . methanol ) to hydrocarbons .
- olefin polymerization oligomerization
- other organic compound conversions such as the conversion of alcohols (e.g . methanol ) to hydrocarbons .
- Example 1 A 22.71 g quantity of 86 % H 3 PO 4 was diluted with 29.3 g H 2 O, followed by the mixing of 10.2 g alpha-alumina monohydrate (i .e. Catapal SB) into the dilute phosphoric acid solution . This slurry was mixed , with stirring , at 25 °C for 10 minutes . To the resulting homogeneous suspension was added 16.3 g of 1 ,7-heptanediamine as directing agent .
- 10.2 g alpha-alumina monohydrate i .e. Catapal SB
- the mixture was transferred to a 300 ml stainless steel autoclave. A 10.42 g quantity of tetraethylorthosilicate was then poured into the autoclave before sealing.
- the reaction mixture prepared had the following composition, in mole ratios:
- R being the 1 ,7-heptanediamine .
- the sealed autoclave was heated for 19 hours at 146°C, then for 4 days at 180°C with stirring at 800 rpm.
- the crystalline product composition was separated from the final liquids by filtration , water washed , and then dried at 110°C.
- the dried product composition was analyzed by X-ray diffraction , proving it to contain the present silicoaluminophosphate composition comprising crystals having large pore windows .
- Table 1 lists the X-ray diffraction pattern of the dried , as-synthes ized , product composition of this example.
- a 23.1 g quantity of 86% H 3 PO 4 was diluted with 70.74 g H 2 O, followed by the mixing of 10.1 g alpha-alumina monohydrate (i .e. Kaiser) into the dilute phosphoric acid solution. This slurry was mixed , with stirring , at 25°C for 10 minutes. To the resulting homogeneous suspension was added 13.02 g of 1 ,7-heptanediamine as directing agent.
- the mixture was transferred to a 300 ml stainless steel autoclave. A 10.41 g quantity of tetraethylorthosilicate was then poured into the autoclave before sealing.
- the reaction mixture prepared had the following composition, in mole ratios:
- SiO 2 /Al 2 O 3 0.5 with R being the 1,7-heptanediamine.
- the sealed autoclave was heated to 200°C and stirred (800 rpm) at this temperature and autogenous pressure for 3 days .
- the crystalline product composition was separated from the final liquids by filtration , water washed , and then dried at 110°C.
- the dried product crystals were analyzed by X-ray diffraction, proving it to be the present silicoaluminophosphate composition comprising crystals having large pore windows .
- Table 2 l ists the X-ray diffraction pattern of the dried, as-synthesized , product of this example.
- Example 3 To further exemplify the present invention, another preparation of the present silicoaluminophosphate was conducted by repeating Example 2, except the directing agent is 1 ,5-pentanediamine.
- the reaction mixture prepared had the composition, in mole ratios:
- SiO 2 /Al 2 O 3 0.5 with R being the 1 ,5-pentanediamine.
- Table 3 lists the X-ray diffraction pattern of the dried, as-synthesized product of this example.
- a 23.1 g quantity of 86 % H 3 PO 4 was diluted with 40 , 74 g H 2 O, followed by the mixing of 10.1 g alpha-alumina monohydrat e (i .e. Catapal SB), and 6.0 g indium nitrate dissolved in 30.0 g H 2 O, into the dilute phosphoric acid solution. This slurry was mixed, with stirring, at 25°C for 10 minutes .
- the reaction mixture prepared had the following composition , in mole ratios :
- M/Al 2 O 3 0.2 with R comprising the 1 ,7-heptanediamine and M comprising indium.
- the sealed autoclave was heated for 19 hours at 146°C, then for 4 days at 180°C with stirring at 400 rpm.
- the crystalline product composition was then separated from the final liquids by filtration, water washed, and then dried at
- the mixture was then transferred to a 300 ml stainless steel autoclave.
- the reaction mixture prepared had the following composition, in mole ratios:
- M/Al 2 O 3 0.2 wi th R comprising the 1 ,5-pentanediamine and M compris ing tin.
- the sealed autoclave was heated' to 200°C and stirred (800 rpm) at this temperature and autogenous pressure for 3 days .
- the crystalline product composition separated from the final liquids by filtration, water washing , and drying at 110°C, produced an X-ray diffraction pattern proving it to be the present metalloaluminophosphate composition comprising crystals having large pore windows .
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Abstract
A crystalline metalloaluminophosphate molecular sieve has the X-ray diffraction lines, (table I), and is crystallized from a reaction mixture comprising a C5-C7 alkyldiamine as directing agent.
Description
SYNTHETIC CRYSTALLINE MOLECULAR SIEVE
AND ITS SYNTHESIS
This invention relates to a synthetic crystalline molecular sieve and to a method of its synthesis.
Zeolitic materials, both natural and synthetic, have been demonstrated in the past to have catalytic properties for various types of hydrocarbon conversion. Certain zeolitic materials are ordered, porous crystalline aluminosilicates having a definite crystalline structure as determined by X-ray diffraction, within which there are a large number of smaller cavities which may be interconnected by a number of still smaller channels or pores. These cavities and pores are uniform in size within a specific zeolitic material. Since the dimensions of these pores are such as to accept for adsorption molecules of certain dimensions while rejecting those of larger dimensions, these materials have come to be known as "molecular sieves" and are utilized in a variety of ways to take advantage of these properties.
Such molecular sieves, both natural and synthetic, include a wide variety of positive ion-containing crystalline aluminosilicates. These aluminosilicates can be described as rigid three-dimensional frameworks of SiO4 and AlO4 in which the tetrahedra are cross-linked by the sharing of oxygen atoms whereby the ratio of the total aluminum and silicon atoms to oxygen atoms is 1:2. The electrovalence of the tetrahedra containing aluminum is balanced by the inclusion in the crystal of a cation, for example an alkali metal or an alkaline earth metal cation. This can be expressed wherein the ratio of aluminum to the number of various cations, such as Ca/2, Sr/2, Na, K or Li, is equal to unity. One type of cation may be exchanged either entirely or partially with
another type of cation utilizing ion exchange techniques in a conventional manner. By means of such cation exchange, it has been possible to vary the properties of a given aluminosilicate by suitable selection of the cation. Prior art techniques have resulted in the formation of a great variety of synthetic zeolites. The zeolites have come to be designated by letter or other convenient symbols, as illustrated by zeolite A (U.S. Patent 2,882,243), zeolite X (U.S. Patent 2,882,244), zeolite Y (U.S. Patent 3,130,007), zeolite ZK-5 (U.S. Patent 3,247,195), zeolite ZK-4 (U.S. Patent 3,314,752), zeolite ZSM-5 (U.S. Patent 3,702,886), zeolite ZSM-11 (U.S. Patent 3,709,979), zeolite ZSM-12 (U.S. Patent 3,832,449), zeolite ZSM-20 (U.S. Patent 3,972,983), zeolite ZSM-35 (U.S. Patent 4,016,245), and zeolite ZSM-23 (U.S. Patent 4,076,842). Aluminum phosphates are taught in, for example, U.S.
Patents 4,310,440 and 4,385,994. These aluminum phosphate materials have essentially electroneutral lattices. U.S. Patent 3,801,704 teaches an aluminum phosphate treated in a certain way to impart acuity. Microporous aluminum phosphates have a composition typified as:
xR:Al2O3: (1.0±0.2)P2O5:yH2O
wherein R is an organic amine or quaternary ammonium salt entrapped within the aluminum phosphate and playing a role as crystallization template, x and y representing the amounts of R and H2O needed to fill the microporous voids. Because the aluminum/phosphorus atomic ratio of these materials is about unity, they display virtually no ion-exchange properties, the framework positive charge on phosphorus being balanced by corresponding negative charge on aluminum:
AlPO4=(AlO2-)(PO2 +)
Silicoaluminophosphates having a variety of structures have also been synthesized, see, for example, Nosa 4,440,871, 4,623,527, 4,639,358, 4,647,442, 4,664,897, 4,639,357 and 4,632,811. Crystalline metalloaluminophosphates are disclosed in U.S. Patent No.4, 713, 227, an antimonophosphoaluminate is disclosed in U.S.
Patent No.4,619, 818 and a titaniumaluminophosphate is disclosed in U.S. Patent No. 4,500,651.
In its broadest aspect, the present invention resides in a synthetic crystalline molecular sieve having the following x-ray diffraction lines:
Interplanar d-Spacing
(A) Relative Intensity (I/Io)
14.980 ± 0.1 vs
12.230 ± 0.1 w
7.493 ± 0.1 w
5.930 ± 0.1 w
4.605 ± 0.05 w
It is to be appreciated that all X -tray diffraction data given herein were collected, with a Scintag diffraction system, equipped with a graphite diffracted beam monachromator and scintillation counter, using copper K-alpha radiation. The K-alpha 2 component of the K-alpha 1-K-alpha 2 doublet was removed with a computer stripping program. The effective X-ray wavelength for the tabulated data is therefore the K-alpha 1 value of 1.5405 Angstroms. 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 d(A) and the relative intensities of the lines, I/Io, where Io 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. The relative intensities are given in terms of the symbols vs = very strong (75-100), s = strong (50-74), m = medium (25-49) and w = weak (0-24). It should be understood that diffraction data listed ffor this sample as single lines may consist
of multiple overlapping lines which under certain conditions, such as differences in crystallite sizes or very high experimental resolution or crystallographic changes, may appear as resolved or partially resolved lines. Typically, 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.
More specifically, the molecular sieve comprises a three-dimensional framework structure composed of tetrahedral units of MO2, AlO2 and PO2, where M is at least one element other than aluminum or phosphorus, and having the following composition: / C
where Q is a cation of valence q, T is an anion of valence t, m is the valence or weighted average valence of the element(s) M, x, y, i and j are numbers satisfying the relationship: z = i-j, and i-j = y-x + (4 + m)(x + y) and z is a number from greater than -1 to less than +1. When z is greater than 0, the metalloaluminophosphate will mostly behave as a cation exchanger with potential use as an acidic catalyst. When z is less than 0, the metalloaluminophosphate will mostly behave as an anion exchanger with potential use as a basic catalyst.
In one preferred embodiment, the element M is silicon alone and the molecular sieve has the following composition:
where 0.01 < x < 1
0.01< y < 1, and x + y < 1
In another embodiment , the element M includes an element other than silicon having an oxidation number of +2 to +6 and an ionic "Radius Ratio" of 0.15 to 0.73 , with the proviso that , when the oxidation number is +2, the Radius Ratio must be 0.52 to 0.62. In some cases , silicon may also be present such that the ratio silicon:non-silicon atoms in the MO2 component is less than 1, preferably less than 0.5.
The term "Radius Ratio" is defined as the ratio of the crystal ionic radius of the element M to the crystal ionic radius of the oxygen anion, 0-2.
The crystal ionic radii of elements are listed in the CRC Handbook of Chemistry and Physics, 61st edition, CRC Press, Inc., 1980, pages F-216 and F-217, said listing incorporated herein by reference. In determining the Radius Ratio, it is necessary to use crystal ionic radii of the M atom and oxygen anion (0-2) which have been measured by the same method.
Non-limiting examples of element M useful herein include:
M Valence Radius Ratio
As +3 0.44
B +3 0.17 Bi +3 0.73
Co +2 0.55
Cu +2 0.54
Fe +2 0.56
Fe +3 0.48
Ge +2 0.55
Ge +4 0.40
In +3 0.61
Mn +2 0.61
Sb +3 0.57
Sn +4 0.54
Ti +3 0.58
Ti +4 0.52
V +3 0.56
V +4 0.48 V +5 0.45
Zn +2 0.56
Non-limiting example of elements not included as M of the present invention include:
Element Valence Radius Ratio B +1 0.26
Ba +1 1.16
Ba +2 1.02
Ce +3 0.78
Cd +1 0.86
Cd +2 0.73
Cr +1 0.61 Cr +2 0.67
Cu +1 0.73
La +1 1.05
Ivfe +1 0.62
Mg +2 0.50
Mo +1 0.70
Sn +2 0.70 Sr +2 0.85
Th +4 0.77
Ti +1 0.73
Ti +2 0.71
Zn +1 0.67
As synthesized , in general, the crystalline composition comprises structural aluminum, phosphorus and element M, and will exhibit an M/(aluminum plus phosphorus) atomic ratio of less than unity and greater than zero, and usually within the range of from 0.001 to 0.99. The phosphorus/aluminum atomic ratio of such materials may be found to vary from 0.01 to 100.0 , as synthesized. It is well recognized that aluminum phosphates exhibit a phosphorus/aluminum atomic ratio of unity, and essentially no element M. Also, the phosphorus-substituted zeolite compositions, sometimes referred to as "aluminosilicophosphate" zeolites, have a silicon/aluminum atomic ratio of usually greater than unity, and generally from 0.66 to 8.0, and a phosphorus/aluminum atomic ratio of less than unity, and usually from 0 to 1.
The molecular sieve of the invention is prepared from a reaction mixture hydrogel containing sources of oxides of aluminum , phosphorus and the non-aluminum, non-phosphorus element M, a directing agent R, and water and having a composition , in terms of mole ratios , within the following ranges:
Broad Preferred Most Prfer
P2O5/AI2O3 0.01 to 20 0.2 to 5 0.5 to 2
H2O/AI2O3 2 to 400 5 to 200 10 to 100
H+/AI2O3 0.01 to 30 0.5 to 20 1 to 10 R/Al2O3 0.01 to 20 0.1 to 10 0.5 to 5
M/AI2O3 0.01 to 20 0.1 to 10 0.5 to 5
where R is a C5 - C7 alkyldiamine, such as , for example, pentanediamine, e .g . 1 ,5-pentanediamine and heptanediamine, e.g . 1 ,7-heptanediamine.
Suitable reaction conditions include a temperature of 80°C to 300°C for a period of time from 5 hours to 20 days. A more preferred temperature range is from 100°C to 200°C with a crystallization time of 24 hours to 10 days. The reaction of the gel particles is carried out until crystals form. The solid product comprising the desired metalloaluminophosphate is then recovered from the reaction medium, such as by cooling the whole to room temperature , filtering and water washing .
The synthesis may be facilitated when the reaction mixture comprises seed crystals , such as those having the structure of the product crystals . The use of at least 0.01%, preferably about 0.10% , and even more preferably about 1% seed crystals (based on total weight) of crystalline material in the reaction mixture will facilitate crystallization in the present method.
The organic directing agent used in the synthesis of the molecular sieve of the invention can be removed to allow access to its internal pore structure by calcining in conventional manner , e.g. at 200 - 550°C for 1 - 48 hours .
While the improved crystalline composition of the present invention may be used as a catalyst component in a wide variety of organic compound, e.g. hydrocarbon compound, conversion reactions, it is notably useful in the processes of cracking, hydrocracking, isomerization and reforming. Other conversion processes for which the present composition may be utilized as a catalyst component include, for example, dewaxing.
The crystalline metalloaluminophosphate composition prepared in accordance herewith can be used either in the as-synthesized form, the hydrogen form or another univalent or multivalent cationic form. It can also be used in intimate combination with a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed. Such components can be exchanged into the composition, impregnated therein or physically intimately admixed therewith. Such components can be impregnated in or on to the crystalline composition such as, for example, by, in the case of platinum, treating the material with a platinum metal-containing ion. Suitable platinum compounds for this purpose include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex. Combinations of metals and methods for their introduction can also be used. The present composition, when employed either as an adsorbent or as a catalyst in a hydrocarbon conversion process, should be dehydrated at least partially. This can be done by heating to a temperature in the range of 65°C to 315°C in an inert atmosphere, such as air or nitrogen, and at atmospheric or subatmospheric pressures for between 1 and 48 hours. Dehydration can be performed at lower temperature merely by placing the zeolite in a vacuum, but a longer time is required to obtain a particular degree of dehydration.
As in the case of many catalysts, it may be desirable to incorporate the hereby prepared metalloaluminophosphate with another material resistant to the temperatures and other conditions employed in certain organic conversion processes. Such matrix materials include active and inactive materials and synthetic or naturally occurring zeolites as well as incorganic materials such as clays, silica and/or metal oxides, e.g. alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates, sols or gels including mixtures of silica and metal oxides. Use of a material in conjunction with the present metalloaluminophosphate, i.e. combined therewith, which is active, may enhance the conversion and/or selectivity of the catalyst in certain organic conversion processes. Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate or reaction. Frequently, crystalline catalytic materials have been incorporated into naturally occurring clays, e.g. bentonite and kaolin. These materials, i.e. clays, oxides, etc., function, in part, as binders for the catalyst. It is desirable to provide a catalyst having good crush strength, because in a petroleum refinery the catalyst is often subjected to rough handling, which tends to break the catalyst down into powder-like materials which cause problems in processing.
Naturally occurring clays which can be composited with the hereby synthesized metalloaluminophosphate include the montmorillonite and kaolin families which include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays, or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
In addition to the foregoing materials, the crystals hereby synthesized can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria,
sϊlica-beryllia , silica-titania , as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix can be in the form of a cogel . A mixture of these components could also be used .
The relative proportions of finely divided crystalline material and matrix vary widely with the crystalline material content ranging from 1 to 90 percent by weight, and more usually in the range of 2 to 50 percent by weight of the composite. Employing a catalyst comprising the composition of this invention containing a hydrogenation component, reforming stocks can be reformed employing a temperature between 450°C and 550°C. The pressure can be between 445 and 3550 kPa (50 and 500 psig), but is preferably between 890 and 2170 kPa (100 and 300 psig). The liquid hourly space velocity is generally between 0.1 and 10 hr-1, preferably between 1 and 4 hr-1 and the hydrogen to hydrocarbon mole ratio is generally between 1 and 10, preferably between 3 and 5.
A catalyst comprising the present composition can also be used for hydroisomerization of normal parrffins, when provided with a hydrogenation component, e.g. platinum. Hydroisomerization is carried out at a temperature between 250°C to 450°C, preferably 300°C to 425°C, with a liquid hourly space velocity between 0.1 and 10 hr-1, preferably between 0.5 and 4 hr-1, employing hydrogen such that the hydrogen to hydrocarbon mole ratio is between 1 and 10. Additionally, the catalyst can be used for olefin or aromatics isomerization employing temperatures between 0°C and 550°C.
A catalyst comprising the metalloaluminophosphate of this invention can also be used for reducing the pour point of gas oils. This process is carried out at a liquid hourly space velocity between 0.1 and 5 hr-1 and a temperature between 300°C and 425°C.
Other reactions which can be accomplished employing a catalyst comprising the composition of this invention containing a metal, e.g. platinum, include hydrogenation-dehydrogenation
reactions and desulfurization reactions , olefin polymerization (oligomerization) , and other organic compound conversions such as the conversion of alcohols (e.g . methanol ) to hydrocarbons . In order to more fully illustrate the nature of the invention and the manner of practicing same , the following examples are presented .
Example 1 A 22.71 g quantity of 86 % H3PO4 was diluted with 29.3 g H2O, followed by the mixing of 10.2 g alpha-alumina monohydrate (i .e. Catapal SB) into the dilute phosphoric acid solution . This slurry was mixed , with stirring , at 25 °C for 10 minutes . To the resulting homogeneous suspension was added 16.3 g of 1 ,7-heptanediamine as directing agent .
The mixture was transferred to a 300 ml stainless steel autoclave. A 10.42 g quantity of tetraethylorthosilicate was then poured into the autoclave before sealing.
The reaction mixture prepared had the following composition, in mole ratios:
P2O5/Al2O3 = 1 .0
H2O/AI 2O3 = 20
H+/AI2O3 = 8.0
R/Al2O3 = 0.5
SiO2/Al2O3 = 0.5
with R being the 1 ,7-heptanediamine .
The sealed autoclave was heated for 19 hours at 146°C, then for 4 days at 180°C with stirring at 800 rpm.
The crystalline product composition was separated from the final liquids by filtration , water washed , and then dried at 110°C. The dried product composition was analyzed by X-ray diffraction , proving it to contain the present silicoaluminophosphate composition comprising crystals having large pore windows . Table 1 lists the X-ray diffraction pattern of the dried , as-synthes ized , product composition of this example.
Table 1
Interplanar Observed Relative d-Spacings (A) 2xTheta Intensities (I/Io)
16.261 5.435 35.4
15.016 5.885 100.0
14.248 6.203 8.3
12.704 6.958 0.9
8.152 10.852 1.9
7.503 11.794 12.9
5.306 16.707 3.9
4.830 18.366 4.9
4.598 19.300 5.2
3.459 25.749 1.1
2.751 32.544 2.7
2.743 32.643 2.9
2.649 33.831 1.4
Example 2
A 23.1 g quantity of 86% H3PO4 was diluted with 70.74 g H2O, followed by the mixing of 10.1 g alpha-alumina monohydrate (i .e. Kaiser) into the dilute phosphoric acid solution. This slurry was mixed , with stirring , at 25°C for 10 minutes. To the resulting homogeneous suspension was added 13.02 g of 1 ,7-heptanediamine as directing agent.
The mixture was transferred to a 300 ml stainless steel autoclave. A 10.41 g quantity of tetraethylorthosilicate was then poured into the autoclave before sealing.
The reaction mixture prepared had the following composition, in mole ratios:
P2O5/AI2O3 = 1.0
H2O/AI2O3 = 40 H+/Al2O3 = 4.1
R/AI2O3 = 1.0
SiO2/Al2O3 = 0.5 with R being the 1,7-heptanediamine.
The sealed autoclave was heated to 200°C and stirred (800 rpm) at this temperature and autogenous pressure for 3 days .
The crystalline product composition was separated from the final liquids by filtration , water washed , and then dried at 110°C. The dried product crystals were analyzed by X-ray diffraction, proving it to be the present silicoaluminophosphate composition comprising crystals having large pore windows . Table 2 l ists the X-ray diffraction pattern of the dried, as-synthesized , product of this example. Table 2
Interplanar Observed Relative d-Spacings (A) 2xTheta Intensities (I/Io)
29.635 2.982 0.5
14.970 5.903 100
12.223 7.232 3
9.843 8.984 1
9.312 9.497 1
8.717 10.146 0.5
7.484 11 .824 5
6.691 13.232 1
5.927 14.946 1
5 .551 15 .963 0.5
5.377 16.485 0.5
4.967 17.854 0.5
4.828 18.374 1
4.601 19.290 1
4.421 20.081 1
4.313 20.588 1
4.178 21.261 0.5
4.023 22.093 0.5
3.970 22.393 0.5
3.792 23.454 0.5
3.732 23.840 0.5
3.508 25.384 0.5
3.446 25.854 0.5
3.354 26.576 1
3.025 29.521 0.5
2.991 29.864 0.5
2.945 30.344 0.5
2.920 30.608 0.5
2.792 32.046 0 .5
2.746 32.598 0.5
2.632 34.062 0.5
A quantity of the as-synthesized composition of this example was calcined at 300°C in air for 3 hours and also analyzed by X-ray diffraction. The results of this analysis proved the product hereof to be structurally stable to thermal treatment.
Example 3 To further exemplify the present invention, another preparation of the present silicoaluminophosphate was conducted by repeating Example 2, except the directing agent is 1 ,5-pentanediamine. The reaction mixture prepared had the composition, in mole ratios:
P2O5/Al2O3 = 1.0
H2O/Al2O3 = 40 H+/Al2O3 = 4.1
R/Al2O3 = 1.0
SiO2/Al2O3 = 0.5 with R being the 1 ,5-pentanediamine.
Crystallization, separation and drying of product was completed as in Example 2. The dried product crystals , analyzed by
X-ray diffraction, proved to be the present silicoaluminophosphate composition comprising crystals having large pore windows . Table 3 lists the X-ray diffraction pattern of the dried, as-synthesized product of this example.
Table 3
Interplanar Observed Relative d-Spacings (A) 2xTheta Intensities (I/Io)
14.980 5 .90 100
12. 230 7.23 3
9.860 8.97 1
9.316 9.49 1
8.706 10.16 1
7.493 11.81 5
6.695 13.22 1
5.930 14.94 2
5.597 15 .83 1
5.385 16.46 1
4.981 17.81 1
4.828 18.38 1
4.605 19.27 1
4.425 20.06 1
4.317 20.57 1
4.180 21.25 1
4.029 22.06 1
3.973 22.38 1
3.767 23.62 1
3.731 23.85 1
3.512 25.36 1
3.446 25 .86 1
3.400 26.21 1
3.356 26.56 1
3.028 29.50 1
Example 4
A 23.1 g quantity of 86 % H3PO4 was diluted with 40 , 74 g H2O, followed by the mixing of 10.1 g alpha-alumina monohydrat e (i .e. Catapal SB), and 6.0 g indium nitrate dissolved in 30.0 g H2O, into the dilute phosphoric acid solution. This slurry was mixed, with stirring, at 25°C for 10 minutes .
To the resulting homogeneous suspension was added 13.0 g of 1 ,7-heptanediamine as directing agent . The mixture was then transferred to a 300 ml stainless steel autoclave. The reaction mixture prepared had the following composition , in mole ratios :
P2O5/AI2O3 = 1 .0 H2O/AI 2O3 = 40
H+/AI2O3 = 4
R/AI2O3 = 1.0
M/Al2O3 = 0.2
with R comprising the 1 ,7-heptanediamine and M comprising indium.
The sealed autoclave was heated for 19 hours at 146°C, then for 4 days at 180°C with stirring at 400 rpm.
The crystalline product composition was then separated from the final liquids by filtration, water washed, and then dried at
110°C. Samples of the dried product crystals and calcined (500°C in air for 3 hours) crystals, were analyzed by X-ray diffraction, and found to be the present metalloaluminophosphate composition comprising crystals having large pore windows. A quantity of the as-synthesized composition of this example, analyzed for chemical composition, had the following components :
Component Wt .%
C 13.44
N 4.27
Al 13.07
P 14.62
M+Si 9.99
Ash 71.42
Example 5
A 23.1 g quantity of 86% H3PO4 was diluted with 40.74 g
H2O, followed by the mixing of 10.1 g alpha-alumina monohydrate
(i.e. Kaiser), and 4.29 g tin sulfate dissolved in 30.0 g H2O, into the dilute phosphoric acid solution (Sn being +4 valence in this solution under these conditions). This slurry was mixed, with stirring, at 25°C for 10 minutes.
To the resulting homogeneous suspension was added 25.5 g of 1,5-pentanediamine as directing agent.
The mixture was then transferred to a 300 ml stainless steel autoclave. The reaction mixture prepared had the following composition, in mole ratios:
P2O5/Al2O3 = 1.0
H2O/AI2O3 = 40
H+/AI2O3 = 4
R/AI2O3 = 1.0
M/Al2O3 = 0.2
wi th R comprising the 1 ,5-pentanediamine and M compris ing tin.
The sealed autoclave was heated' to 200°C and stirred (800 rpm) at this temperature and autogenous pressure for 3 days .
The crystalline product composition , separated from the final liquids by filtration, water washing , and drying at 110°C, produced an X-ray diffraction pattern proving it to be the present metalloaluminophosphate composition comprising crystals having large pore windows .
A quantity of the composition of this example, calcined at 300°C in air for 3 hours , was also analyzed by X-ray diffraction .
The results of this analysis proved the product to be structurally stable to thermal treatment .
Claims
1. A synthetic crystalline molecular sieve haying the following X-ray diffraction lines:
Interplanar d-Spacing
(A) Relative Intensity (I/In)
14.980 ± 0.1 vs
12.230 ± 0.1 w
7.493 ± 0.1 w
5.930 ± 0.1 w
4.605 ± 0.05 w
2. The molecular sieve of claim 1 and comprising a threedimensional framework structure composed of tetrahedral units of MO2, AlO2 and PO2, where M is at least one element other than aluminum or phosphorus, and having the following composition:
3. The molecular sieve of claim 2 wherein M is silicon alone and the molecular sieve has the following composition:
0.01 < y < 1, and x + y < 1
4. The molecular seive of claim 2 wherein M includes an element other than silicon having an oxidation number +2 and an ionic radius ratio of 0.52 to 0.62 or an oxidation number of +3 to +6 and an ionic radius ratio of 0.15 to 0.73.
5. A molecular sieve of claim 4 wherein M includes In3+, Sb3+, Sn4+, Ti3+ or Ti4+.
6. The molecular sieve of claim 4, wherein M also includes silicon such that the ratio of siliconmon-silicon atoms in the MO2 component is less than 1.
7. A method for synthesizing the molecular sieve of claim 2 comprising the steps of preparing a reaction mixture comprising sources of Al2O3, P2O5, an oxide of M, water and an organic directing agent R having a composition within the following ranges:
P2O5/Al2O3 0.01 to 20
H2O/AI2O3 2 to 400
H+/AI2O3 0.01 to 30
R/AI2O3 0.01 to 20
M/AI2O3 0.01 to 20
wherein R is a C5-C7 alkyldiamine, (ii) maintaining said mixture under sufficient conditions until crystals of said molecular sieve are formed and (iii) recovering said crystalline molecular sieve from step (ii).
8. The method of claim 7 wherein said mixture has the following composition ranges:
P2O5/AI2O3 0.2 to 5
H2O/AI2O3 5 to 200
H+/AI2O3 0.5 to 20
R/AI2O3 0.1 to 10
M/AI2O3 0.1 to 10
9. The method of claim 7 wherein said directing agent R is 1,7-heptanediamine or 1,5-pentanediamine.
10. The method of claim 7 wherein said conditions include a temperature of 80-300°C for 5 hours to 20 days.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019890702092A KR900700386A (en) | 1988-03-10 | 1989-02-27 | Synthetic crystalline molecular sieve and method for synthesizing it |
DK214990A DK214990A (en) | 1988-03-10 | 1990-09-07 | SYNTHETIC CRYSTALLINIC MOLECULE OIL AND PROCEDURE FOR PREPARING THIS |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/166,571 US4913796A (en) | 1988-03-10 | 1988-03-10 | Novel crystalline silicoaluminophosphate |
US166,571 | 1988-03-10 | ||
US07/166,585 US4913795A (en) | 1988-03-10 | 1988-03-10 | Novel crystalline metalloaluminophosphate |
US166,585 | 1988-03-10 |
Publications (1)
Publication Number | Publication Date |
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WO1989008608A1 true WO1989008608A1 (en) | 1989-09-21 |
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PCT/US1989/000824 WO1989008608A1 (en) | 1988-03-10 | 1989-02-27 | Synthetic crystalline molecular sieve and its synthesis |
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EP (1) | EP0437429A1 (en) |
JP (1) | JPH03503276A (en) |
KR (1) | KR900700386A (en) |
AU (1) | AU3197989A (en) |
DK (1) | DK214990A (en) |
NZ (1) | NZ228228A (en) |
WO (1) | WO1989008608A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0425029A2 (en) * | 1989-10-27 | 1991-05-02 | Shell Internationale Researchmaatschappij B.V. | Crystalline aluminophosphates |
EP0431660A2 (en) * | 1989-11-24 | 1991-06-12 | Shell Internationale Researchmaatschappij B.V. | Crystalline aluminophosphates and related compounds |
EP0483927A2 (en) * | 1990-11-02 | 1992-05-06 | Shell Internationale Researchmaatschappij B.V. | Crystalline aluminophosphates and related compounds |
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-
1989
- 1989-02-27 EP EP89903006A patent/EP0437429A1/en not_active Withdrawn
- 1989-02-27 JP JP1502795A patent/JPH03503276A/en active Pending
- 1989-02-27 AU AU31979/89A patent/AU3197989A/en not_active Abandoned
- 1989-02-27 KR KR1019890702092A patent/KR900700386A/en not_active Application Discontinuation
- 1989-02-27 WO PCT/US1989/000824 patent/WO1989008608A1/en not_active Application Discontinuation
- 1989-03-06 NZ NZ228228A patent/NZ228228A/en unknown
-
1990
- 1990-09-07 DK DK214990A patent/DK214990A/en not_active Application Discontinuation
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US4139600A (en) * | 1977-04-22 | 1979-02-13 | Mobil Oil Corporation | Synthesis of zeolite ZSM-5 |
US4296083A (en) * | 1977-04-22 | 1981-10-20 | Mobil Oil Corporation | Zeolite synthesis |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0425029A2 (en) * | 1989-10-27 | 1991-05-02 | Shell Internationale Researchmaatschappij B.V. | Crystalline aluminophosphates |
EP0425029A3 (en) * | 1989-10-27 | 1992-02-05 | Shell Internationale Research Maatschappij B.V. | Crystalline aluminophosphates and related compounds |
EP0431660A2 (en) * | 1989-11-24 | 1991-06-12 | Shell Internationale Researchmaatschappij B.V. | Crystalline aluminophosphates and related compounds |
EP0431660A3 (en) * | 1989-11-24 | 1992-02-26 | Shell Internationale Research Maatschappij B.V. | Crystalline aluminophosphates and related compounds |
EP0483927A2 (en) * | 1990-11-02 | 1992-05-06 | Shell Internationale Researchmaatschappij B.V. | Crystalline aluminophosphates and related compounds |
EP0483927A3 (en) * | 1990-11-02 | 1992-11-19 | Shell Internationale Research Maatschappij B.V. | Crystalline aluminophosphates and related compounds |
US5232683A (en) * | 1990-11-02 | 1993-08-03 | Shell Oil Company | Crystalline aluminophosphates and related compounds |
Also Published As
Publication number | Publication date |
---|---|
KR900700386A (en) | 1990-08-13 |
AU3197989A (en) | 1989-10-05 |
DK214990D0 (en) | 1990-09-07 |
EP0437429A1 (en) | 1991-07-24 |
DK214990A (en) | 1990-09-07 |
NZ228228A (en) | 1990-09-26 |
JPH03503276A (en) | 1991-07-25 |
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