CA1217178A - Titanium-containing molecular sieves - Google Patents
Titanium-containing molecular sievesInfo
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- CA1217178A CA1217178A CA000450658A CA450658A CA1217178A CA 1217178 A CA1217178 A CA 1217178A CA 000450658 A CA000450658 A CA 000450658A CA 450658 A CA450658 A CA 450658A CA 1217178 A CA1217178 A CA 1217178A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3408—Regenerating or reactivating of aluminosilicate molecular sieves
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- 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
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/2206—Catalytic processes not covered by C07C5/23 - C07C5/31
- C07C5/222—Catalytic processes not covered by C07C5/23 - C07C5/31 with crystalline alumino-silicates, e.g. molecular sieves
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
- C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
- C07C5/41—Catalytic processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/065—Catalytic reforming characterised by the catalyst used containing crystalline zeolitic molecular sieves, other than aluminosilicates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
Abstract
TITANIUM-CONTAINING-MOLECULAR SIEVES
ABSTRACT
Titanium-containing molecular sieves are disclosed having use as molecular sieves and as catalyst compositions in hydrocarbon conversion and other processes.
ABSTRACT
Titanium-containing molecular sieves are disclosed having use as molecular sieves and as catalyst compositions in hydrocarbon conversion and other processes.
Description
~2~78 TITANIUM-CONTAINING MOLECULAR SIEVES
Field of the Invention The present invention relates to a class of crystalline microporous molecular sieves to the method for their preparation, and to their use as adsorbent~ and ~a~alysts. These compositions are prepa~ed hydrothermally from ~els containing rea~tive phosphorus, aluminum and titanium compounds and an organic ~empla~ing agent~s).
Background of the ~nvention The existence of molecular sieves of th~
~rystalline aluminosilicate type are well known to the art with numerous species having been found, both as naturally occurring m~terials and as synthetically formed materials. Numerous instances of the existence of these materials may be found in the art relating thereto and such will not be discussed herein.
The existence of crystalline microporous ~compositions which are o~her ~han zeolites, i.e., other than aluminosilicates, have been reported heretoforea For example, U.S. Patent No. 4,310,440 discloses a novel family of crys~alline, microporous crystalli~e aluminophosphate compositions.
Further, numerous patents have been obtained in compo~itions wherein me~al and non-metal oxides have been deposited sn an aluminosilic3te.
For example, U~S. Patent No. 4,358,397 discloses a modified zeolite ~aluminosilicate) which has been modified to have at l*a~t 0~25 weight percent of one or more Group IV A ~e~als incorporated into ~he zeolite in the oxide form and at least 0.25 we~ht ~-13,854 ~d1~
~2~
Field of the Invention The present invention relates to a class of crystalline microporous molecular sieves to the method for their preparation, and to their use as adsorbent~ and ~a~alysts. These compositions are prepa~ed hydrothermally from ~els containing rea~tive phosphorus, aluminum and titanium compounds and an organic ~empla~ing agent~s).
Background of the ~nvention The existence of molecular sieves of th~
~rystalline aluminosilicate type are well known to the art with numerous species having been found, both as naturally occurring m~terials and as synthetically formed materials. Numerous instances of the existence of these materials may be found in the art relating thereto and such will not be discussed herein.
The existence of crystalline microporous ~compositions which are o~her ~han zeolites, i.e., other than aluminosilicates, have been reported heretoforea For example, U.S. Patent No. 4,310,440 discloses a novel family of crys~alline, microporous crystalli~e aluminophosphate compositions.
Further, numerous patents have been obtained in compo~itions wherein me~al and non-metal oxides have been deposited sn an aluminosilic3te.
For example, U~S. Patent No. 4,358,397 discloses a modified zeolite ~aluminosilicate) which has been modified to have at l*a~t 0~25 weight percent of one or more Group IV A ~e~als incorporated into ~he zeolite in the oxide form and at least 0.25 we~ht ~-13,854 ~d1~
~2~
- 2 --pe~ cent of phosphorus incorporated into the zeolite in the oxide form of phosphorus. The term "incorporation" is clarifi~d in column 2, beginning at line 8 as being a "...treatment with a compound derived from one or more elements of Group IV A of the Periodic Table of Elements (i . e., Ti , 2r and Hf) to yield a composite conta.ining a minor proportion of an oxide of ~uch element~" Similarly, the zeolites are disclosed as beirlg treated with a phosphorus-containing compound to deposit a minor proport;on of an oxide of phosphorus.
Although there has been an extensive treatment in the patent art and in the published literature of aluminosilicates and recently, aluminophosphates, there has been little information available on the presence of other than such materials. This is particularly true in the area of titanium containing compositions wherein titanium is present in the framework of the molecular sieve or so intimately related as to change the physical and/or chemical characteristics of the molecular sieve. This is understandable in the question of aluminosilicates, as indicated by the article, ~Can Ti4 replace si4~ in silicates? n 7 Mineralogi~al Magaxine, September ~ol 37~ No. 287, pages 366-369 ~1969). In this article it is concluded that substitution of framework ~ilicon by titanium does not usually occur in aluminosilicates owing ~o ~he preference of titanium to be octahedrally bound rather than tetrahedrally bound. The formation vf crystalline ntitanosilica~e zeolites~n is disclosed ~Obviou ~ product i5 not a zeolite since i~ is not an aluminosilica~e.
~-13,854 7~
z
Although there has been an extensive treatment in the patent art and in the published literature of aluminosilicates and recently, aluminophosphates, there has been little information available on the presence of other than such materials. This is particularly true in the area of titanium containing compositions wherein titanium is present in the framework of the molecular sieve or so intimately related as to change the physical and/or chemical characteristics of the molecular sieve. This is understandable in the question of aluminosilicates, as indicated by the article, ~Can Ti4 replace si4~ in silicates? n 7 Mineralogi~al Magaxine, September ~ol 37~ No. 287, pages 366-369 ~1969). In this article it is concluded that substitution of framework ~ilicon by titanium does not usually occur in aluminosilicates owing ~o ~he preference of titanium to be octahedrally bound rather than tetrahedrally bound. The formation vf crystalline ntitanosilica~e zeolites~n is disclosed ~Obviou ~ product i5 not a zeolite since i~ is not an aluminosilica~e.
~-13,854 7~
z
3 --~n V.S. Pa~en~ ~o. 3,32~,4Bl, wherein ~
metallo-~ ilicate c:omplex is foit~ed and tre!ated to give the titanc~silicate product. ~he evid~n~e for the ~laimed t~tan~s~lica~e i~ bzsed on the X ray powder d~f fr~c~ n pat~esn da~ he X-ray d~ta are . omewha~ suspect a~ to whether ~uch ~how ~ubst~tution of ~ n~um ~nto ~be ~ilicate fr~mework inasmu~h ~s the claimed X~ray patterns are also ob~erved for the zircon~um ~ ates ~nd by the f~
that similar X-ray p~ttern~ showing fiimil~r ln~erplanar dist~nceg ~r the tw~ v~lue~ in pa~gerns B3 have been reported for ~ilicali~e. (~ee &B
2,071,071 A~ ~
The incorporation of tit~r ium in a ~ilical~te type ~ructure ~ disclo~ed in GB
2,071,071 A, publ~shed December 21, 197g. The amount of titanium elaim2d ~co be ~ub~itu~ed into ~he ~ ate-type ~truc~ure ~ ve~y small, being no more than 0.04 mole pe~en~, b~sed Oll the numher oP
moles of ~ilica~ and may ibe as low ~s O.OOû5~. ~he titanium content was det~rmined by Ghemical ~naly~is and was no~c de~cermined ~co be grezlter ~han 0. 023 ~n any ~se, As indic~t~d by a c:~mpa~ i~ors o~ Fig . la ~nd ~ig. lb, the ~moun~ ~f t~tanium pre~en~ mall ~nd no ~ignific~n~ ehange in ~he X-r~y dif fra~t~on pattern of ilieallt~ was observed an~ ltbe minor ~hzlnge~ observed may $imply be ~ue to occlu~ed ~ nium dioxideO grhus, ~bsent other ~nalyti~al d~ca the ~eult~ alre no~ ~ell defined. No comparison ~ata for ti~an~ um diox~de ~re di~cl~d D
~ ~n ~ew of ~h~ ~bov~ clear ~ha~ ~h~ ~
3ubstitut~0n ~f ~ nium lnto a zeoli~ yl?e framework ~; esnce~v~ to be p~s~ble, where~in tit~nium ~ub~t~tLlte~ 1~r ~ cont bu~ f~ul~ o~
-D-13 p854 I ." .
. . .
7~
proof. The substitution of titanium in non-zeoli~ic materials has not hereto been disclosed although a number of minerals have been found to contain titanium (see: "Can Ti Replace Si in Silicates"~
supra)~ Further, although titanium has been postulated to substitute for silicon in the aluminosilicate framewoxk it has not heretofore been considered as to what occurs when silicon is not present. Specifically, these questions have not heretofore been considered in the art with respect to titanium substitution in aluminophosphate molecular sievPs and such is the subject of the instant invention.
BRIEF DESCRIPTION OF THE DRAWINGS
.. . .. . _ _ . _ . _ _ _ _ FIG. 1 is a ternary diagram wherein parameters relating to the instant compositions are set forth as mole fractions.
FIG. 2 is a ternary diagram wherein parameters relating to preferred compositions are set forth as mole fractions.
FIG. 3 is a ternary diagram wherein parameters relating to the reac~ion mixtures emplsyed in the preparation of the compositions of this invention are set forth as mole fractions.
:! '.
- 4a -Summary o~_the Invention The present invention relates to titanium-containing molecular sieves comprising a three-dimensional microporous crystal framework structure of [TiO2], [A102~ and [P02]
tetrahedral units which has a unit empirical Eormula on an anhydrous basis of:
mR : (TiXAlyPæ)02 ll) wherein "R'l represents at least one organic templating agent present in ~he intracrystalline pore system; "m" represents the moles o~ "R" present per mole of (TiXAlyPz)02 and has a value of between zero and about 5Ø, the maximum value in each case depending upon the molecular dimensions of the templating agent and ~he available void volume of pore system of the particular titanium molecul~r ,~ieve; x", "y" and ~z" represent the mole fractions of titanium, aluminum and phosphorus, respectively, present as tetrahedral oxides~ said mole fractions being such tha~ they are within the pentagonal .g.
~2~
compositional area defined by points A, B, C, D and E of the ternary, said di~gram which is Fig. 1 of the drawings, points A, B, C, D and E repr~senting the following values for ~x"~ "y" and ~z~:
Mole_Fraction Point x y z A 0.0010.45 0.549 B 0.880.01 0.11 C 0.980.01 ~.01 D 0.290.70 OL 01 E 0.0010.70 0.299 The parameters ~x~, ny" and "z~ are preferably within the pentago~al compositional area defined by points a, b, c 7 d and e of the ternary diagram which is Fig. 2 of the drawings, said points a, b, c, d and e representing the following values for "x~, ny"
and ~z":
M~le ~racci~n Po_ X ~ Z
a 0.0020.499 0.499 b 0.200.40 0.40 c ~.200.50 0.30 d 0.100.60 0.30 e 0.0020.60 0.398 The molecular sieves of the present invention are generally employable as catalysts or various hydrocarbon ~onversion processes, Detailed Descri~ion of the Invention Th~ present invention relates to titanium-containing mole~ular sieves comprising a hree-dimensional microporous crys~al framework structure of [TiO23~ 1AlO2~ and lPO2]
tetrahedral units whi~h has a unit empirical formula on an anhydrous basis o$:
~R : tTiXAlyPz)O2 (1) D-13,854 7t~
wherein ~R" represents at lea~t one organic templating agent present in the intracrystalline pore system; "m" represents the moles of ~R~ present per mole of ~Ti~AlyP~)O2 and has a value of betwee~ æero and about 5Ø, the maximum value in each cas~ depending upon the molecular dimensions of ~he ~emplating agen~ and ~he available void volume of pore system of the particular titanium molecular sieve; ~x", ~y~ and "z" represent the mole fractions of titanium, aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D and E representing the following values for "x", ~y" and n _o le r Point x _y_ z A 0.001 0.45 0.549 ~ 0.88 0.01 ~.11 C 0.98 0.01 0.01 D 0.29 0.70 0.01 E 0.001 0.70 0.299 The parameters "x~, ~y~ and "z" are preferably within the pentagonal compositional area defined by points a, b, c~ d and e of the ternary diagram which is Fig. 2 of the drawings, said points a, b, , d and e representing the following values for "xn, "y~
and ~z~:
Mole Fraction _ Point x _y_ z a 0.002 0.499 0.499 b . 0.20 0.40 0~40 c 0.20 ~.~0 0~30 d 0.10 ~.60 0.30 e 0~002 0.60 0.398 D-~3,854 7~
The molecular sieves of the present invention are generally employable as catalysts for various hydrocarbon conversion processes.
The molecular sieves employed in the instant process will be referred to hereinafter, solely for poin~ of reference herein as nTAPO"
molecular sieves, or as "TAPOs" if the reference is to the class as a whole~ This designation is simply made for the sake of convenient reference herein and is not meant to designate a particular structure for any given TAPO molecul~r sieve. The members of the class of TAPO's employed hereinafter in ~he examples will be characterized simply by referring to such members as TAPO-~7 TAPO-ll, etc, i.e., a particular species will be referred to as TAPO-n where "n" is a number specific to a ~iven class member as its preparation is reported herein~ Thi~ designation is an arbitrary one and is not intended to denote structural relationship to another material(s~ which may also be ~haracterized by a numberin~ system.
The term "unit empirical formula" is used herein according to its common meaning to designate the simplest eormula which ~ives the relative number of ~oles of titanium, aluminum and phosphorus whi~h form th2 lTiO2~ lP023 and [A10~ t~trahedral unit within a titanium-containing molecular sieve and which forms the molecular ~ramework of ~he TAPO
composition(sl. The unit empirical formula is given in ~erms of ti~anium, aluminum and phosphorus as shown in Formula 11~, above~ and does no~ include other compounds~ cations or anions which may be present as a result of the preparation or the ~xistence of other impurities or ~aterials in the bulk compos~tion not containing the aforementioned D-13,854 7~
_ tetrahedral unit. The amount of template R is reported as part of the composition when the as-synthesized unit empirical formula is given, and water may also be reported unless such is defined as the anhydrous form. For convenience, coefficient "m" for template "R" is reported as a value that is normalized by dividing the number of moles of organic by the total moles of titanium, aluminum and phosphorus.
The unit empirical formula for a given TAPO
can be calculated using the chemical analysis data for that TAPO. Thus, for example, in the preparation of TAPO-ll disclosed hereinafter in Example 9, the overall composition of the as-synthesized TAPO-ll is calculated using the chemical analysis data and expressed in terms of molar oxide ratios on an anhydrous basis as:
0~29 (n(Pr)NH) : 0.095 : A1203 : 0.92 P205 The unit empirical formula for the as-synthesized TAPO-ll composition on an anhydrous basis is:
o.074(n(Pr)NH): (Tio 024Alo,sogPo.468~02 using the aforementioned formula form of mR : (SiXAlyPz)02 This unit empirical as-synthesized formula is readily computed from the molar oxide ratio expression in which the components [n(Pr)NH~, Ti, Al and P are present in the molar ratio of:
0.29R : 0.995Ti : 2.OAl : 1.84P
The sum (Ti + Al ~ P) = (0.095 ~ 2.0 + 1.~4) = 3.935 normalized to (Ti + Al + P~ ~ 1.00 by dividing each term by 3.935, thusly: m=(0.29/3.935~ = 0.074; x =
(0.095/3.935) = 0.024; y = (2.0/3.935) = 0.508; and z = (1.84/3.935) = 0.~68.
The unit empirical formula for a TAPO may be given on an "as-synthesized" basis or may be D-13,854-C
~L2~
given after an "as-synthesized" T~PO composition has been subjected to 50me post treatment process, e.g., calcination. The term "as-synthesized" herein shall be used to refer to the TAPO composition(s) formed as a result of the hydrothermal crystallization but before the TAPO composition has been subjected to post ~reatment to remove any volatile components present therein~ The actual value of "m" for a pos~-treated TARO will depend on several fa~tors ~including: the particular TAPO~ template, severity of the post-treatment in terms of its ability to remove the template from the TAPO, the proposed application of the TAPO composition, and etc.) and the value for ~m" can be within the range of values as defined for the as-synthesized TAPO compositions although 6uch is generally less than ~he as-synthesized TAPO unless such post trea~ment process adds template to the TAPO so treated. A
TAPO composition which is in the calcined or oth~r post-treatment form generally has an empirical formula represented by Formula ~1), except that the value o~ ~mn is generally less than about 0.02~
Under sufficiently severe post-treatment conditions, e.g. roasting in ~ir at high ~emperature for long periods (over 1 hr.), the value of "m" may be zero ~0) or, in any even~, ~he ~emplate, ~, is undet~table by normal analytical procedures~
Th~ molecular sieves o the presen~
invention are generally further characterized by an intracrystalline adsorption capacity for water at
metallo-~ ilicate c:omplex is foit~ed and tre!ated to give the titanc~silicate product. ~he evid~n~e for the ~laimed t~tan~s~lica~e i~ bzsed on the X ray powder d~f fr~c~ n pat~esn da~ he X-ray d~ta are . omewha~ suspect a~ to whether ~uch ~how ~ubst~tution of ~ n~um ~nto ~be ~ilicate fr~mework inasmu~h ~s the claimed X~ray patterns are also ob~erved for the zircon~um ~ ates ~nd by the f~
that similar X-ray p~ttern~ showing fiimil~r ln~erplanar dist~nceg ~r the tw~ v~lue~ in pa~gerns B3 have been reported for ~ilicali~e. (~ee &B
2,071,071 A~ ~
The incorporation of tit~r ium in a ~ilical~te type ~ructure ~ disclo~ed in GB
2,071,071 A, publ~shed December 21, 197g. The amount of titanium elaim2d ~co be ~ub~itu~ed into ~he ~ ate-type ~truc~ure ~ ve~y small, being no more than 0.04 mole pe~en~, b~sed Oll the numher oP
moles of ~ilica~ and may ibe as low ~s O.OOû5~. ~he titanium content was det~rmined by Ghemical ~naly~is and was no~c de~cermined ~co be grezlter ~han 0. 023 ~n any ~se, As indic~t~d by a c:~mpa~ i~ors o~ Fig . la ~nd ~ig. lb, the ~moun~ ~f t~tanium pre~en~ mall ~nd no ~ignific~n~ ehange in ~he X-r~y dif fra~t~on pattern of ilieallt~ was observed an~ ltbe minor ~hzlnge~ observed may $imply be ~ue to occlu~ed ~ nium dioxideO grhus, ~bsent other ~nalyti~al d~ca the ~eult~ alre no~ ~ell defined. No comparison ~ata for ti~an~ um diox~de ~re di~cl~d D
~ ~n ~ew of ~h~ ~bov~ clear ~ha~ ~h~ ~
3ubstitut~0n ~f ~ nium lnto a zeoli~ yl?e framework ~; esnce~v~ to be p~s~ble, where~in tit~nium ~ub~t~tLlte~ 1~r ~ cont bu~ f~ul~ o~
-D-13 p854 I ." .
. . .
7~
proof. The substitution of titanium in non-zeoli~ic materials has not hereto been disclosed although a number of minerals have been found to contain titanium (see: "Can Ti Replace Si in Silicates"~
supra)~ Further, although titanium has been postulated to substitute for silicon in the aluminosilicate framewoxk it has not heretofore been considered as to what occurs when silicon is not present. Specifically, these questions have not heretofore been considered in the art with respect to titanium substitution in aluminophosphate molecular sievPs and such is the subject of the instant invention.
BRIEF DESCRIPTION OF THE DRAWINGS
.. . .. . _ _ . _ . _ _ _ _ FIG. 1 is a ternary diagram wherein parameters relating to the instant compositions are set forth as mole fractions.
FIG. 2 is a ternary diagram wherein parameters relating to preferred compositions are set forth as mole fractions.
FIG. 3 is a ternary diagram wherein parameters relating to the reac~ion mixtures emplsyed in the preparation of the compositions of this invention are set forth as mole fractions.
:! '.
- 4a -Summary o~_the Invention The present invention relates to titanium-containing molecular sieves comprising a three-dimensional microporous crystal framework structure of [TiO2], [A102~ and [P02]
tetrahedral units which has a unit empirical Eormula on an anhydrous basis of:
mR : (TiXAlyPæ)02 ll) wherein "R'l represents at least one organic templating agent present in ~he intracrystalline pore system; "m" represents the moles o~ "R" present per mole of (TiXAlyPz)02 and has a value of between zero and about 5Ø, the maximum value in each case depending upon the molecular dimensions of the templating agent and ~he available void volume of pore system of the particular titanium molecul~r ,~ieve; x", "y" and ~z" represent the mole fractions of titanium, aluminum and phosphorus, respectively, present as tetrahedral oxides~ said mole fractions being such tha~ they are within the pentagonal .g.
~2~
compositional area defined by points A, B, C, D and E of the ternary, said di~gram which is Fig. 1 of the drawings, points A, B, C, D and E repr~senting the following values for ~x"~ "y" and ~z~:
Mole_Fraction Point x y z A 0.0010.45 0.549 B 0.880.01 0.11 C 0.980.01 ~.01 D 0.290.70 OL 01 E 0.0010.70 0.299 The parameters ~x~, ny" and "z~ are preferably within the pentago~al compositional area defined by points a, b, c 7 d and e of the ternary diagram which is Fig. 2 of the drawings, said points a, b, c, d and e representing the following values for "x~, ny"
and ~z":
M~le ~racci~n Po_ X ~ Z
a 0.0020.499 0.499 b 0.200.40 0.40 c ~.200.50 0.30 d 0.100.60 0.30 e 0.0020.60 0.398 The molecular sieves of the present invention are generally employable as catalysts or various hydrocarbon ~onversion processes, Detailed Descri~ion of the Invention Th~ present invention relates to titanium-containing mole~ular sieves comprising a hree-dimensional microporous crys~al framework structure of [TiO23~ 1AlO2~ and lPO2]
tetrahedral units whi~h has a unit empirical formula on an anhydrous basis o$:
~R : tTiXAlyPz)O2 (1) D-13,854 7t~
wherein ~R" represents at lea~t one organic templating agent present in the intracrystalline pore system; "m" represents the moles of ~R~ present per mole of ~Ti~AlyP~)O2 and has a value of betwee~ æero and about 5Ø, the maximum value in each cas~ depending upon the molecular dimensions of ~he ~emplating agen~ and ~he available void volume of pore system of the particular titanium molecular sieve; ~x", ~y~ and "z" represent the mole fractions of titanium, aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D and E representing the following values for "x", ~y" and n _o le r Point x _y_ z A 0.001 0.45 0.549 ~ 0.88 0.01 ~.11 C 0.98 0.01 0.01 D 0.29 0.70 0.01 E 0.001 0.70 0.299 The parameters "x~, ~y~ and "z" are preferably within the pentagonal compositional area defined by points a, b, c~ d and e of the ternary diagram which is Fig. 2 of the drawings, said points a, b, , d and e representing the following values for "xn, "y~
and ~z~:
Mole Fraction _ Point x _y_ z a 0.002 0.499 0.499 b . 0.20 0.40 0~40 c 0.20 ~.~0 0~30 d 0.10 ~.60 0.30 e 0~002 0.60 0.398 D-~3,854 7~
The molecular sieves of the present invention are generally employable as catalysts for various hydrocarbon conversion processes.
The molecular sieves employed in the instant process will be referred to hereinafter, solely for poin~ of reference herein as nTAPO"
molecular sieves, or as "TAPOs" if the reference is to the class as a whole~ This designation is simply made for the sake of convenient reference herein and is not meant to designate a particular structure for any given TAPO molecul~r sieve. The members of the class of TAPO's employed hereinafter in ~he examples will be characterized simply by referring to such members as TAPO-~7 TAPO-ll, etc, i.e., a particular species will be referred to as TAPO-n where "n" is a number specific to a ~iven class member as its preparation is reported herein~ Thi~ designation is an arbitrary one and is not intended to denote structural relationship to another material(s~ which may also be ~haracterized by a numberin~ system.
The term "unit empirical formula" is used herein according to its common meaning to designate the simplest eormula which ~ives the relative number of ~oles of titanium, aluminum and phosphorus whi~h form th2 lTiO2~ lP023 and [A10~ t~trahedral unit within a titanium-containing molecular sieve and which forms the molecular ~ramework of ~he TAPO
composition(sl. The unit empirical formula is given in ~erms of ti~anium, aluminum and phosphorus as shown in Formula 11~, above~ and does no~ include other compounds~ cations or anions which may be present as a result of the preparation or the ~xistence of other impurities or ~aterials in the bulk compos~tion not containing the aforementioned D-13,854 7~
_ tetrahedral unit. The amount of template R is reported as part of the composition when the as-synthesized unit empirical formula is given, and water may also be reported unless such is defined as the anhydrous form. For convenience, coefficient "m" for template "R" is reported as a value that is normalized by dividing the number of moles of organic by the total moles of titanium, aluminum and phosphorus.
The unit empirical formula for a given TAPO
can be calculated using the chemical analysis data for that TAPO. Thus, for example, in the preparation of TAPO-ll disclosed hereinafter in Example 9, the overall composition of the as-synthesized TAPO-ll is calculated using the chemical analysis data and expressed in terms of molar oxide ratios on an anhydrous basis as:
0~29 (n(Pr)NH) : 0.095 : A1203 : 0.92 P205 The unit empirical formula for the as-synthesized TAPO-ll composition on an anhydrous basis is:
o.074(n(Pr)NH): (Tio 024Alo,sogPo.468~02 using the aforementioned formula form of mR : (SiXAlyPz)02 This unit empirical as-synthesized formula is readily computed from the molar oxide ratio expression in which the components [n(Pr)NH~, Ti, Al and P are present in the molar ratio of:
0.29R : 0.995Ti : 2.OAl : 1.84P
The sum (Ti + Al ~ P) = (0.095 ~ 2.0 + 1.~4) = 3.935 normalized to (Ti + Al + P~ ~ 1.00 by dividing each term by 3.935, thusly: m=(0.29/3.935~ = 0.074; x =
(0.095/3.935) = 0.024; y = (2.0/3.935) = 0.508; and z = (1.84/3.935) = 0.~68.
The unit empirical formula for a TAPO may be given on an "as-synthesized" basis or may be D-13,854-C
~L2~
given after an "as-synthesized" T~PO composition has been subjected to 50me post treatment process, e.g., calcination. The term "as-synthesized" herein shall be used to refer to the TAPO composition(s) formed as a result of the hydrothermal crystallization but before the TAPO composition has been subjected to post ~reatment to remove any volatile components present therein~ The actual value of "m" for a pos~-treated TARO will depend on several fa~tors ~including: the particular TAPO~ template, severity of the post-treatment in terms of its ability to remove the template from the TAPO, the proposed application of the TAPO composition, and etc.) and the value for ~m" can be within the range of values as defined for the as-synthesized TAPO compositions although 6uch is generally less than ~he as-synthesized TAPO unless such post trea~ment process adds template to the TAPO so treated. A
TAPO composition which is in the calcined or oth~r post-treatment form generally has an empirical formula represented by Formula ~1), except that the value o~ ~mn is generally less than about 0.02~
Under sufficiently severe post-treatment conditions, e.g. roasting in ~ir at high ~emperature for long periods (over 1 hr.), the value of "m" may be zero ~0) or, in any even~, ~he ~emplate, ~, is undet~table by normal analytical procedures~
Th~ molecular sieves o the presen~
invention are generally further characterized by an intracrystalline adsorption capacity for water at
4.6 torr and about 24C of about 3.0 weight percentO The adsorpti~n of water has been observed to be complete.ly reversible while retaining the same essential framework tQpology in both the hydrated and dehydrated ~tate. The ter~ "essential ramework D 13,~54 L7~
topology~ is meant to designate ~he spatial arrangement of the primary bond linkages. A lack of change in the framework topology indicates that there is no disruption of these primary bond linkages.
The molecular sieves of the instant invention are generally synthesized by hydrothermal crystallization from a reaction mixture comprising reactive sources of titanium, aluminum and phosphorus, and one or more organic templating agents. OptionallyO alkali metal(s) may be present an the reaction ~ixture~ The reaction mixture is placed in a pressure vessel, preferably lined with an iner~ plastic material, such as polytetrafluoroethylene, and heated, preferably under the autogenous pressure, at a temperature of at least ~bout 100C, and preferably between lOO~C
and 250C, until crystals of the molecular sieve product are obtained, usually for a period of from 2 hours to 2 weeks. While not essential to the synthesis of the in~tant molecular sieves, it has been found that in general stirring or other moderate agitation of the reaction mixture and/or seeding ~he reaction mixture with seed crystals of either the TAPO to be produced~ or a topologically similar composition, facilitates the crystalli~ation procedure. The product is recovered by any convenient method such as centri~ugation or filtration.
After crystallization the TAPO may be isolat~d and washed with water and dried in air~ As a result of thP hydrothermal crystalliza~ion~ the as-synthesized TAPO contains wi~hin its intracrystalline pore system at least one form of D-13,854 .~
7~
~the template employed ln its formation. Gen2rally, the template ~ a molecul~r Rpecies, but $ i~
possibl~, steric ~onsideration~ permittin~, that ~S
least ~ome of the ~emplate ~ presen~ a~ ~
~harge-bal~ncing ~ation. ~enera~ly the template is too l~rge to move freely through the ~n~racry~t~ ne pore ~ys~em of the ormed TAPO ~nd may be removed by ~ post-treatmen~ pro~ess, ~uch a~
by calcining the T~PO ~t temperatur2s of be~ween ~bou~ 200C ~d to about 700C ~ ~s ~o ~hermally degrade the ~mplate or by employing ~me other post-trea~ment process for removal of ~ leas~ part of the template from the TAP~. In ~ome ins~ances the pores ~f the ~APO are ~uff~ciently large ~G
permit tran~port of ~he t~mplate, and, ~c~ordingly, complete or part~l removal ~hcreof ~an be accomplished by conven~on~l desorption procedures such as carr~ed out in ~he case ~f 2eolites~
The TAP0~ ~re preferably formed from a reaction mixtur~ having ~ m~le frac~ion o~ alkali metal ~ti~n which ~s ~ufficiently low th~t it does not ~nterf~r~ with the formation ~ the TAP~
compD~ition. The TAPO com~ositions ~re generally formed ~om ~ r~act~on mixtuge containing re~c~ive ~ources ~f T~O2~ A12~3~ ~nd ~25 organic ~emplat~ng agent, ~aid reaction mixture co~pris~ng ~ composition expr~se~ ln terms of ~olar oxide r~tios ofs ~ R2o-~TixAl~p~1o2-9 ~2 wher~in ~R~ ~ an organi~ ~cmplating ~gen~; hf ~ has v~lue l~rge ~nough to eonsti~u~@ an effe~ive amoun~ of ~R~ ~aid affe~tiYe amount being h~
~mount ~h~ch for~s said TAP0 compositions; "g" has a ~alue ~ r~m zero ~o 500~ ~x~, ~y~ ~nd ~z~
D-139~5 ~ ' ~7~78 - ~2 -represent the mole fractions, respectively of titanium, aluminum and phosphorus in the (TiXAlyPz)O2 constituent, and each has a value of at least 0.001 and being within the quatrilatera~ compositional area defined by points, h, i, j and k which is Fig. 3 of the drawings, said points h, i, j and k representing the following values for nxn ny~ and nzn:
Mole Fraction Point x y z h 0~001 0.989 0.01 i 0.001 0.01 0.989 j 0.32 ~.24 0.44 k 0.98 0.01 0.01 Although the TAPO compositions will form if higher concontrations of alkali metal cation are present, such reaction mixtures are not generally preferred. A reaction mixture, expressed in terms of molar oxide ratios, comprising the following bulk composition is pref~rred:
R2 WM2'(TixAlyPz)2 nH2 wherein ~" is an organic template; "On has a valu~
great enough to constitute an effective concentration of ~R" and is preferably within ~he range-of from greater than zero ~0) ~o abou~ 5.0;
~M" is an alkali m~tal cation ~w~ has a value of from z~ro to 2.5; Wn~ has a value between about zero (0) and about 500; ~x~ ~y~ and ~zw repres~nt the ~ol~ frac~ions, respectively, of ~itanium~ aluminum and phosphorus in ~TiXAlyPz~O2 ~x~, ~y" and wz~ represent ~he mole fractions, re~pectively of titanium~ ~luminum and phosphorus in the ~TiXAlyP~)O~ constituent, and each has ~
value of at least O.U01 and being within the D-13,854 , quatrilateral compositional area defined by points, h, i, j and k which is Fig. 3 of the drawings, ~aid points h, i, j and k representing the following values for "xn, "y~ and ~zw Mole Fraction Point x z_ h 9.001 0.g890.01 o.oal 0.010.9~9 j 0.32 0.2~0.44 k 0.98 0.010.01 When ~he TAPOs are ~ynthesized by this me~hod ~he value of ~mn ~n Formula (1) is generally above about 0.02.
Though the presence of alkali metal cations is not preferred, when they are present in ~he reaction mix~ure i~ is preferred ~o first admix a~
leas~ a portion ~.g. at lea~t abou~. 10 weight percent) o~ each of the aluminum and phosphorus sourc~s in the ~ubstant;al absen~e (e.g. preferably less than about 20 percent of the total weight of the aluminum source and phosphorus source) of the ._titanium sourc~. Thi~ proc:edure avoids adding 'che phosphorus ~ource to za S~asic r~action mix~ur~
containlng the itanium sour~e and aluminum source t ~as was done in mo~t of the publi~hed at~emp~s l:o subst~tute isomorphously 11?021 tetrahedra for ~io;!~ ~e~rahedra in zeoli~ic tructure~3.
Although the r~action mechanis~n is by no means clear ~t thi~ t~m~, the unc~on of the template may be to faYor ~he incorpor~tion of lP02] ~nd [A10;2]
tetrahedra ln the ~ramework ~tructures of the cry~talline products with ~TiOz] tetrahedra isomorphously replacing EPO;~] te~rahedra.
D-13 ,8 54 ~4 .
; 1~
The reaction mixture fr~m which these TAPOs are formed contain on~ or more organic templating agentfi ~templates) which can be m~st any of ~hose heretofore proposed :Eor use in the synthesis of ~luminosilicates and aluminopho~pha~es. The template preferably contains at least one element of Group VA of the Periodic Table, particularly nitrogen, phosphorus, arsenic and/or antimony, more preferably nitrogen or phosphorus and mos~
preferably nitrogen and are of the ~ormula R~X
wherein X i~ ~elec~d from the group ronsisting of nitrogen, phosphorus, arsenic and/or antimony and R
may be hydrogen, alkyl, aryl, araalkyl, or alkylaryl group and is preferably aryl or alkyl containing between 1 ~nd 8 carbon atoms, although more than eight carbon atoms may be present in WR~ of group o the template. Nitrogen-containing templates are preferred, including amines and quaternary ammonium compounds, the latter being represented generally by ~he formula R'4N~ wherein each R' is an alkyl, aryl, alkylaryl, or araalkyl group; wherein R' preferably contains from 1 to 8 carbon atoms or higheE when R' is alkyl and greater than 6 carbon a~oms when Rl i8 oth~rwise t as hereinbefore di~cussed~ Polymeric quaternary ammonium salts ~uch [(Cl~H32N23 tOH)2jX wherein ~x~ has a ~alue of at leas~ 2 ~ay also be employed~ The mo~o-, di- ~nd ~ri~amines, ~ w luding mixed aminest may also be employe~ as templates ei~her alone or in ~ombination with a quaternary ammonium compound or another template~ The exa~t relationship of various template~ when ~oncurren~ly employed i5 no~ ~learly underctood. Mixture~ o~ wo or more templati~g agent~ can produce e~ her mixture~ of TAPOs or in D-13,~54 the instan~e where one template is more strongly directing than another template the more ~trongly directing template may control the course of the hydrothermal crystallization wherein with the o~her template serving primarily to establish the pH
conditisns of the reaction mixture.
Representative template~ include tetramethylammonium, etraethylammonium, tetrapropylammonium or tetrabutylammonium ions;
di n-propylamin~ tripropylamin~; ~riethylamine;
triethanolamine; piperidine; cyclohexylamine;
2-methylpyridine; N~N-dimethylbenzylamine;
die~hylethanolamine; ~icyclohexylamine;
N,N-dimethylethanolamine; 1,4-dia~abicyclo (2,2,2 octane; N-methyldiethanolamine, N-methyl-ethanolamine; N-methylcyclohexylamine; 3-methyl-pyridine; 4~methylpyridine; quinuclidine;
N,N'-dimethyl-1,4-diazab~cyclo (2t2,2) octane ion;
di-n-butylamine, neopentylamine; di-n-pentylamine;
isopropylamine t~bu~ylamine; e~hylenediamin~;
pyrrolidine; and 2-imidazolidone. As will be readily apparent from the illustrativ2 examples ~e~
forth hereinafter, not every ~emplate will produ~e ~very TAP0 composit~on although a ~inyle emplate can, with proper selection of the reaction ~ondi~ions, ~ause ~he forma~ion of different ~PO
compositions, and a ~iven TAPO composition can be produ~ed using diferent template~.
In those instance~ where an aluminum alkoxide is the reac~iYe aluminum ~ource, ~he corresponding alcohol i~ necessarily presen in ~he reaction mix~ure sin~e it ~ a hydrolysis product of the alkoxideO I t has not a~ yet been determined whether ~his alcohol participat~s in the ~yn~hesis D-13,854 '~ff~
~ 16 -process a5 a templatlng agent, or in some other function and, a~cordingly, is not reported as a template in the unit formula of the TAPOs, although such may be acting as templates.
Alkali metal cations if present in the reaction mixture may facilitate the crystallization of certaln TAPO phases, although the exact func~ion of ~uch cations, when present, in crystallization, if an~ not presently known. Alkali cations present in the reaction mixture generally appear in the formed TAPO composi~ion, either as occluded (extraneous) cations and/or as structural cations balancing net negative charges a~ various sites in the crystal lattice~ It should be understood tha~
although the unit formula for the TAPOs does not spe~ifically recite the presence o alkali cations they are not excluded in the same sense that hydrogen ~ations a~d/or hydroxyl groups are not specifically provided for in the traditional formulae for zeolitic aluminosilicates.
Mo~t any reactive titanium source may be employed herein. The preferred reactive titanium sources include ~itanium alkoxidesl water-soluble titanates and titanium chelates.
Most any reactive phosphorous source may be employed. Phosphori~ acid is ~he most sui~able phosphorus source employed ko da~e. Accordingly~
other acids of phosphorus are generally believed to be ~uitable phospho~us sources for use herein.
O~ganic phospha~es such as ~riethyl phosphate have been ~ound ~atisfac~ory, and ~o also have crystalline or amorphous aluminophosphases such as the AlPO~ composi~ions of U.S.P. 4,3109440.
Organo-phosphorus ~ompounds, ~uch as D-13,854 tetra~utyl-phosphonium bromide have not, apparently, served as reactive sources of phosphorus, but these compounds do function as templating agents and may also be capable of being suitable phosphorus sources under proper process conditions (yet to be ascertained). Organic phosphorus compounds, e.g.
esters, are believed to be generally suitable since they can generate acids of phosphorus ln situ.
Co~ventional phosphorus salts, such as sodium metaphosphate, may be used, at least in part as the phosphorus source, but they are not preferred.
Most any reactive aluminum source may be employed herein. The preferred reactive aluminum sources include aluminum alkoxides, such as aluminum isopropoxide, and pseudobeohmite. Crystalline or amorphous aluminophosphates which are a suitable source of phosphorus are, of course, also suitable sources of aluminum. Other sources of aluminum used in zeolite synthesis, such as gibbsite, sodium aluminate and aluminum trichloride, can be employed but are generally not preferred.
Since the e~act nature of the TAPO
molecular sieves o the present invention is not clearly understood at present, although all are believed to contain [TiO2] tetrahedra in the three-dimensional microporous crystal framework structure, it is advantayeous to characterize ~he TAPO molecular sieves by means of their chemical composition. This is due to the low level of titanium present in certain of the instant molecular sieves prepared to date which makes it difficult to ascertain the exact nature of the interaction between titanium, aluminum and phosphorus. ~s a result, although it is believed that titanium, D-13,8~4-C
L7~
l~iO2]~ has substituted isomorphously ~or lAlO2]
or [PQ2] tetrahedra, it is appropriate to characterize certain TAPO compositions by reference to their chemical ~omposition in terms of the m~le ratios of oxides in the as-synthesized and anhydrous ~orm as:
vR . pTiO2 : ~A123 rP2 5 wherein ~R~ represents at leas~ one organic templating agent present in the intracrystalline pore ~y~tem; ~va represent~ ~n effectiv~ amount of the organi~ templat~ng agent to orm said TAPO
compositions and preferably has a value between and in~luding zero and about 3.0; ~p~ 9 ~qW and ~r~
represent moles, respectively; of titanium, alumina and phosphorus pentaoxide, based o~ said moles being ~u~h that hey are within the pen agonal compositional area defined by point A, B, C, D and E
of the ternary diagram which is Fig. 1 of the drawings, said points A, B, C, D and E representing the following values for ~p~, ~q~ and ~r~.
Point ~ 5_ r A . 0~304 1.0 1.22 B 176 lrO 11~0 C 196 1.0 1.0 D 0.828 1.0 0.0143 E . 0O003 1.0 OJ427 The parameters ~p~, ~q~ and "r" are prefera~ly within the pentagonal compositional area defined by points a" b, c, d and e of the ternary diagram which is Fig. 2 of the drawings, said points a, b, c, d and e representing 'che following values for ~Ip~ y ~"
and ~r":
D-13 ~854 Mole Point p q r a 0.008 1.0 1.0 b 1.0 1.0 1.0 c 0.80 1.0 0.60 d 0.333 1.0 0.50 e 0.067 1.0 0.663 The TAPO compositions of this invention have unique surface characteristics making them useful as molecular sieves and as catalyst or as bases for catalysts in a variety of separation, hydrocarbon conversion and oxidative combustion processes. The TAPO composition can be impregnated or otherwise associated with catalytically active metals by the numerous methods known in the art and used, for example, in fabricating catalyst compositions containing alumina or aluminosilicate materials.
TAPO's may be employed for separating molecular species in admixture with molecular species of a different degree of polarity or having different kinetic diameters by con~acting such mixtures with a T~POSs) having pore diameters large enough to adsorb at least one but not all molecular species of the mixture based on the polarity of the adsorbed molecular species and/or its kinetic diameter. When TAPOs are employed for such separation processes the TAPOs are at least partiall~ activated whereby some molecular species selectively enter the intracrystalline pore system thereof.
The hydrocarbon conversion reactions catalyzed by TAPO compositions include cracking, hydrocracking; alkylation of both the aromatic and isoparaffin typ~s; isomerization (including xylene D-13,854-C
,"~, .
.i. c .
~7~
isomerization); polym~rization; reforming;
hydrogenation; dehydrogenation; transalkylation;
dealkylation; and hydration.
When a TAPO containing catalyst composition contains a hydrogenation promoter, such promoter may be platinum, palladium, tungsten, nickel or molybdenum and may be used to treat various petroleum stocks including heavy petroleum residual stocks, cyclic stocks and other hydrocrackable charge stocks. These stocks can be hydrocracked at temperatures in the range of between about 400F and about B25F using molar ratios of hydrogen to hydrocarbon in the range of b~tween about 2 and about 80, pressures between about 10 and about 3500 p.s.i.g., and a liquid hourly space velocity tLHSV) of between about 0.1 and about 20, preferably between about 1.0 and about 10.
TAPO containing catalyst compositions may also be employed in reforming processes in which the hydrocarbon feedstocks contact the catalyst at temperatures between about 700F and about 1000F, hydrogen pressures of between about 100 and about 500 p.s.i.g., LHSV values in the range between about 0.1 and about 10 and hydrogen to hydrocarbon molar ratios in the range between about 1 and about 20, preferably between about 4 and about 12.
Further, TAPO containing catalysts which contain hydrogenation promoters, are also use~ul in hydroisomerization processes wherein the feedstock(s), such as normal paraffins, is converted to saturated branched-chain isomers.
Hydroisomerization processes are typically carried out at a temperature be~ween about 200F and a~out 600F, preferably between about 300F and about D-13,354-C
,4 `
550F with an L~SV value between about 0.2 and about 1Ø Hydrogen is typically supplied to the reactor in admixture with the hydrocarbon feedstock in molar proportions of hydrogen to the feeds~ock of between about 1 and about 5.
TAPO-containin~ compositions similar to those employed for hydrocracking and hydroisomerization may also be employed at between about 650F and about 1000F, preferably between about 850F and about 950F and usually at somewhat lower pressures within the range between about 15 and about 50 p.s.i.g. for the hydroisomerization of normal paraffins. Pre~erably the paraffin feedstock comprises normal paraffins having a carbon number range of C7-C20. The contact time between the feedstock and the TAPO containing catalyst is generally relatively short to avoid undesirable side reactions such as olefin polymerization and paraf~in cracking. LHSV values in the range between about o.l and about 10, preferably between about 1.0 and about 6.0 are suitable.
The low alkali metal content (often not measurable by current analy-tical techniques) o~ the instant TAPO compositions make them particularly ~ell suited for use in the conversion of alkylaromatic compounds, particularly for use in the catalytic disproportionation o~ toluene, xylene, trimethylbenzenes, tetramethylbenzenes and the like. In such disproportio.nation processes it has been obser~ed that isomerization and transalkylation can also oc~ur. The TAPO-containiny catalysts ~or such processes will typically include Group VIII
noble metal adjuvants alone or in conjunction with Group VI-B metals such as tungsten, molybdenum and D-13,~5~-C
chromium which are preferably included in such catalyst compositions in amounts between about 3 and about 15 weight percent of the overall catalyst composition. ~xtraneous hydrogen can, but need not be present in the reaction zone which is maintained at a temperature between about 400 and about 750F, pressures in the range between about 100 and about 2000 p.s.i.g. and LHSV values in the range between about 0.1 and about 15.
TAPO containing catalysts may be employed in catalytic cracking processes wherein such are preferably amployed with feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residues etc. with gasoline being the principal desired product. Temperature conditions are typically between about 850 and about 1100F, LH~V values between about 0.5 and about 10 pressure conditions are between about 0 p.s.i.g. and about 50 p.s.i.g.
TAPO containing catalysts may be employed for dehydrocyclization reactions which employ paraffinic hydrocarbon feedstocks, preferably normal paraffins having more than 6 carbon atoms, to form benzene, xylenes, toluene and the like.
Dehydrocyclization processes are typically carried out using reaction conditions similar to those employed for catalytic cracking. For such processes it is preferred to use a Group VIII non-noble metal cation such as cobalt and nickel in conjunction with the TAPO com~osition.
TAPO containin~ catalysts may be employed in catalytic dealkylation where paraf~inic side chains are cleaved from aromatic nuclei without substantially hydrogenating the ring structure at relatively high temperatures in the range between D-13,854-C
7i~
about 80~F and about 1000F at moderate hydrogen pressures between about 300 and about lO00 p.s.i.g.
with other conditions being similar to those described above for catalytic hydrocracking. TAPO
containing catalysts for catalytic dealkylation are of the same type described above in connection with catalytic dehydrocyclization. Particularly desirable dealkylation reactions contemplated herein include the conversion of methylnaphthalene to naphthalene and toluene and/or xylenes to benzene.
TAPO containing catalysts may be used in catalytic hydrofining wherein the primary objective is to provide for the selective hydrodecomposition of organic sulfur and/or nitrogen compounds without substantially affecting hydrocarbon molecules present therewith. For this purpose it is preferred to employ the same general conditions described above for catalytic h~drocracking. The catalysts are typically of the same general na~ure as described in connection with dehydrocyclization operations. Feeds-tocks commonly employed for catalytic hydroforming include: gasoline fractions;
kerosenes; jet fuel fractions; diesel fractions;
light and heavy gas oils; deasphalted crude oil residua; and the like. The feedstock may contain up to about 5 weight percent of sulfur and up to about 3 weight percent of nitroyen.
TAPO containing catalysts may be employed for isomerization processes under conditions similar to those described above for reforming although isomeriæation processes tend to require somewhat more acidic catalysts than those employed in reforming processes. Olefins are preferably isomerized at temperatures between about 500F and D-13,854-C
- 24 ~
about 9009F, while paraffins, naphthenes and alkyl aromatics are i~omerized at temperatures between about 700F and about 1000F. Particularly desirable isomerization reactions contemplated herein include the conYersion of n-heptane and/~r n~octane t~ l~oheptanes, iso-octanes, butane to iso-butane, methylcyclopentane ~o cylcohexane, meta-xylene and/or ortho-xylene to para-xylene, l-butene to 2-butene and/or isobutene, n-hexene to isohexane, cyclohexane to methylcyclopentene etc.
The preferred ~at~on form i8 a combination of a TAPO
with polyv~lent me~al compounds (such as sulfides) of metal~ of G~oup II A, Group II-B and rare earth metals. For alkylat;on and dealkylation processes TAPO compo~itions haYing pores of a~ least 5A are preferred. When employed for dealkylation of alkyl ~roma~ics, ~he temperature i5 usually at leas~ 350F
and ran~es up to a temperature at which substantial cracking of ~he feedstock or conversion products occurs, generally up to about 700F. The temperature is preferably at leas 450F and not greater than the ~ri~ical temperature of ~he compound undergoing dealkylation. Pressure condi~ions are applied ~o retain a~ least the aromati~ feed in ~he li~uid s~ate. For alkylation ~he ~empera~ure can be ~s low as 250~F but is preferably at least 350Fo In alkylation of benzenet ~oluene and xylene; ~he preferred ~lkylation agents are olefins such as e~hylene and propylene.
The TAPO compositions o this invention may be employed in ~onven~ional molecular sieving processes as here~ofore have been carried out using aluminosilica~e, ~luminophospha~e or other co~monly D-13,8S4 7~7~
- 2~ ~
employed molecular sieves. TAPO composi~ions are preferably activated prior to their use in a molecular sieve process to remove any molecular species which may be present in the ~ntracry~talline pore system as a resul~ of synthesis or otherwise.
For ~he TAPO compositions this is somet;mes accompli~hed by thermally destroying the organic species present in an as-synthesized TAPO since such organic species may be too large to be desorbed by.
convent~onal mean~.
The TAPO compositions of this inve~tion are also use~ul as adsorbents and are capable of ~eparating mixtures of m~lecular speci~s both on the basis of molecular size (kine~ic diameters) and based on the degree of polari y of the molecular ~pel-ies. When the separation of molecular species ~s based upon th~ selec~ive adsorption based on molecular size, the TAPO is chosen in ~iew of the dimensions of its pores such that at least the ~mallest molecular specie of the mixture can enter the intraGry~talline void space while at leas~ the large~t specae i~ excluded. When the separation i based on degree of polarity it is generally the case that the m~re hydrophali~ ~PO will preferen i~lly adsorb ~he more p~lar molecular speGies of a mixture haYing different degrees of pol~rity even though both molecular ~pecie~ ~an communicate with the pore ~ystem of the TAPD.
The instant TAPO compositions may b~
fur~her eharacteri ~ed and dis'cinguished from alu~inoph~s~hate~ by reference to the ca~alytic propertles exhiLbited by th~ TAPO çompos~tions. When the T~PO compositions are tested ~or n- butane crackin~ and compared wit~h aluminophosphate D-13, 854 ~f~7~
- 2~ -compositions having a similar topology it has been observed tba~ the TAPO compositions are more active ~atalysts as indicated by a higher numerical value iEor n-butane cracking. ~rhis comparison will be discussed hereinafter in the examples 38 to 46.
The following examples are provided to exemplify the invention and are not meant to be limiting thereof in any way.
(a) ~xample~ 1 to 20 were carried out to demonstrate the preparation of the TAPO compositions of this invention. The TAPO compositions were ~ar~ied out by hydrothermal crystallization procedure discussed ~upra~ Reaction mixtures were prepared for each exampl~, unless otherwise noted, using titanium source (titanium isoproproxide; 95 wt percent aqueous solu~ion or ~itanium acetyl acetonate (75 wt % in isopropanol)), aluminum ~ource (eithex aluminum lsoproproxide or a pseudo-boehmite phase, 75.1~ wto % A1203 and 24.9 wt % H20), a ~phosphoru~ ssurce ~85% orthophosphoric acid (H3PO~)) t water and at least one organi~
template.
The method of addition of the above mentioned ~omponen 5 to ~he reaction ~ix~ure was done according to three methods ~A, B and C)7 Method~ A, B and C ~re as follows:
METHOD A
The water and aluminum isoproproxide were blended ~o orm a bomogeneous mixture. Phosphoric acid was added to this mixture and blended to form a homogeneous mix~ur~. The t~i~anium sour~e was added to the above mix~ure and the mixture blend~d ~o form D-13,854 .~ . . .
P homogeneous ~ ure,. ~he organic ~emplating agent ~referred to herein a~ ~emplate~ ) wa added ~o thi~
xture and blended un~il 5 ho~ogeneou~ ~xture was observed c METHOD B
The water ~nd phosphori~ ~cid were blended lto ~orn~ a hb~aogeneou~ ~ixture. The p~eudo-boehm~'ce phase was added t~ hi~ mixture ~nd blended ~o form hsmogeneou m~xture. The t~tanium source was ~dded ~o ~his mix~ure until ~ homogeneou~ mixture was obse~ved. ~he s:~rg~nl~ template w~s adde~ to this ~l~sture ~nd blended until a homogeneous mixg:ur~
was obser~e~.
ETHOD C
The water and pseudo-boehmite were blended to form ~ h~mogen~ou~ ~nixtureO ~he t~t~nium sour~e was ~ded . o ~hi~ m~x~ur~ ~nd blended tc~ form a homogeneous mix~ure. Phosphori~ ~cid was ~ddee to this mix'cure and blended t~ provi~e a homogeneDus mix'cure 3fter ~;hi ::h ~he org~nic t~mpl~te w~s ~dded ~nd ~he ~nixture again blended un~il a ho~nog~neous mixture wa~ obs~rvea.
~ 1~) Example~ 1 to 20 w~re ~ar~ied out ~y pr@parlng reae4~on ~ixtur~s a~ ~bo~ ~e~rib~d, using the amount~ ~t ~or~h in ~ble I~
t~ h@ c~mpos~ n ~ ~h~
~iactur~ of l~xample~ 1 to 20 wer~ ~xpr~ssed in terms o th~ ~ol~r ga~clo o ox~ 1$ fQllOW~
~ sA~203: J?25~Ti~28 ~ ~2 wh~r~n ~R" i~ templ~'cs pr~s~n~ in amoun~ nd 18 the mol~r r~tlo o template t~ mole ~f ~2~
~nd ~ gh~ a~ 2 ~o A1203. q~he ~ cte~ t~flplDte and th~ value~ f~3r n~l w~ ~re ~ o~ bl~
D-13 ~oB541 . ~ . . . . . .
~z~
(d) The reaction mixtures were then each sealed in a stainless steel pressure vessel lined with polytetrafluoroethylene and heated in an oven at a temperature (see Table II) and for a time (see Table II) at the autogeneous pressure. The solid reaction product was recovered by filtration, washed with water and dried at room temperature.
(e) The products obtained in part (d) for Examples 1 to 20 were analyzed by X-ray powder diffraction and characterized to be the TAPO
compositions set forth in Table II.
(f) The X-ray patterns carried out herein and all Gther X-ray patterns appearing herein were obtained using standard x-ray powder diffraction techniques. The radiation source was a high-intensity, copper target, X-ray tube operated at 50 Kv and 40 ma. The diffraction pattern from the copper K radiation and graphite monochromator is suitably recorded by an X-ray spectrometer scintillation counter, pulse height analyzer and strip chart recorder. Flat compressed powder samples are scanned at 2(2 theta) per minute, using a two second time constant. Interplanar spacings (d) in Angstrom units are obtained from the position of the diffraction peaks expressed as 20 (theta) where theta is the Bragg angle as observed on the strip chart. Intensities were determined from the heights of diffraction peaks after subtracting background, IIIol' being the intensity of the strongest line or peak, and "I" being the intensity of each of the other peaks. ~hen Relative Intensities are reported the following abbreviations mean: vs = very strong; s = strong; m = medium, w =
weak; and vw = very weak. Other abbreviations include: sh = shoulder and br = broad.
D-13,854-C
a - 2g As will be understood by those skilled in the art the determination of the parameter 2 theta is subject to bo~h human and mechanical error, which in combination, can impo~e an uncertainty of about l0.4 on each repor~ed value of 2 theta. This ~uncertainty is, of course, also manifested in the reported values of the d-spacinys, which are calculated from the 2 theta valuPs~ This imprecision is general throughout the art and is not ufficient to preclude the differentiation of the present ~ryætalline ma~erials from each o~her and ~rom the compositions of the prior art.
D-13~854 ~ ~2~ ~
o c m m ~ m m m a~~ m m ~ ct m m m m m ~ E
OIl~ I~ oc~ IY~ ~) ~ ~ CO _ N ~ co oo cr~ O~ O ~t ~t ~ ~ E
O a) 3 ~ D a~ ~ ~ tv~ ~ ~ ~ ~ ~ _ ~ ~ _ ,, _ _ _ _ -- -- -- ,,, :
E
V ~ ~ I~ O O O ~ ~ ~
T ~
m ~r x ,_ 1~ ~ C ~ c u v ~ ~
,_ E ,_ Q
E c r~ ~
~t2 ~ r G ~ ~ q ~ ~ ~ ~r ~ ~ ~ ~ ~ ~ ql ,~, , c o _ ~ ~ o ~ U
o 1- a L ~ N ~J N N ~ ~ N ~ G u ~ x "~
O . _ ~ L L
.:t .~, ~ O tll X CL ._ ._ L ~ E
* -- ~r) -- ~ ~ ~; ~ o o o 1~ 1~ 1~ 1~ 1~ ~ c; o ~o O ~ ~ L ~ '~ ~ ._ U
a~ c ~
> , ~ ~ E
2 I T T T I I T _ _ _ T 2 T I I I ~ ~ 2 L L ~ ~
~ ~ e ~ ~o <3C o <ot L L L ~0 0 ~ ~0 ~0 0 L L O ~ 1~ C E E
E ~ C C C 1~ t C C 1-- O ,, ~_ ~ V C
E X 1~ _ _ al LO ~ ~ ~1) _ ~J 1 1 ~ U'l ~D r~ ~ ~ o _ t~l ~ ~ 11'1 ~O 1~ ~ ~` n~ 1-- s i-- 1-- 3 ~ _ . _ _ _ _ ~ ~ ~
X _ ~
~J
.., ,..,, . ~
_ , ., , o g o ~:
L O O O O O O O O O O O O O O O O O O O O ~ ~
o ~r <r a ~ ~ ~ ~ ~ ~ ~ ~ ~ ~, c L ~
s E ,~_ E ^ o, S ~ ~ O O O ~ O q` O ~ O O ~ O O O ~r c Q L V~
E N ~ \1 E L ~ ~ _ C Q Q
O O O O O O O O O O O O O O O O O O O O ~ T IIS 4~
EIr~ O Ll-) O 11~ 0 U') O 10 0 0 Lrl In 11~ Lr) O Ll ) O 1~ 0 (D Z
I_ N -- N ~ N -- N -- N ~ -- -- _ N -- N -- ~J ~ L ~
~¦ C~ L a ~¦ ~ N ~ ~) ~ D ~ ~ ~) ~1 'D '.D r~ ~ ~O ~J ~ ~ Q C
~> OO--C;OOOOOOOOOOOOOOOO
O O I aJ
O O ~ Q
E ~ c ~> 2 2 2 T I O ~ v) C ~
r- 2 2 I I T I ~: 2 -- ^ ^ I T I I I I ~ ~ T Q E ~11 <D O
Q ~ 3 ~ ~ 3 ~ ' ~ ~ ~ ~ L L aJ q~
1~ 1~ 1- 1- C C C 1-- 1- ~ 1- 1- 1~ C C 1-- Q ~ Q
~ T L C~ L
~ ~ ~ a X nE~
E -- ~ tY ~t If) ~ I` C!~ cn o -- N l'') ~ Il') D 1~ CO a~- O
3 N _ N
~2~7~
ra) The products of examples 8, 10, 13 and lB were calcined at 600C~ 550C and 600C and 550C
in air for 1.5, 1.0, 105 and 1DO hour~, re~pecti~ely. The ~APO'~ were then employed to determine adsorption capacities of TAPO-5, TAPO-ll, TAPO-13 ~nd TAPO-31~ respectively~ as prepared in these examplesO The adsorption capacities were measured using a ~tandard McBain-Bakr gravimet~ir adsorpt~on apparatus on ~amples activated in a vacuum at 350~C.
The data for TAPO 5, T~PO-ll~ TAP0-18 and TAP~-31 were as ~11OWS ~nd as ~e~ forth in (b), ~c~, (d) and ~e), hereinater.
(b) TAPO~5:
Kinetic Pr2ssure Temp. wt ~
Diameterj A~ (Torr) (~C) Adsorbed 2 3.46 101 ~lB3 10~6 2 3.46 736 ~183 16.1 Cyclohexane 6~0 4~ 22.9 10.5 Cy~loh~xane h~0 67 22.9 18~6 ~2 2.65 11 22.~ 19.1 ~2 2~65 1~ ~2.~ ~8.3 D-13~54 (c) ~AP0 ~
Kinetic Pressure Temp. wt ~6 Diameter~ A (TorrL ~C) Ad~orbed Q2 3~46 101 lB3 6.7
topology~ is meant to designate ~he spatial arrangement of the primary bond linkages. A lack of change in the framework topology indicates that there is no disruption of these primary bond linkages.
The molecular sieves of the instant invention are generally synthesized by hydrothermal crystallization from a reaction mixture comprising reactive sources of titanium, aluminum and phosphorus, and one or more organic templating agents. OptionallyO alkali metal(s) may be present an the reaction ~ixture~ The reaction mixture is placed in a pressure vessel, preferably lined with an iner~ plastic material, such as polytetrafluoroethylene, and heated, preferably under the autogenous pressure, at a temperature of at least ~bout 100C, and preferably between lOO~C
and 250C, until crystals of the molecular sieve product are obtained, usually for a period of from 2 hours to 2 weeks. While not essential to the synthesis of the in~tant molecular sieves, it has been found that in general stirring or other moderate agitation of the reaction mixture and/or seeding ~he reaction mixture with seed crystals of either the TAPO to be produced~ or a topologically similar composition, facilitates the crystalli~ation procedure. The product is recovered by any convenient method such as centri~ugation or filtration.
After crystallization the TAPO may be isolat~d and washed with water and dried in air~ As a result of thP hydrothermal crystalliza~ion~ the as-synthesized TAPO contains wi~hin its intracrystalline pore system at least one form of D-13,854 .~
7~
~the template employed ln its formation. Gen2rally, the template ~ a molecul~r Rpecies, but $ i~
possibl~, steric ~onsideration~ permittin~, that ~S
least ~ome of the ~emplate ~ presen~ a~ ~
~harge-bal~ncing ~ation. ~enera~ly the template is too l~rge to move freely through the ~n~racry~t~ ne pore ~ys~em of the ormed TAPO ~nd may be removed by ~ post-treatmen~ pro~ess, ~uch a~
by calcining the T~PO ~t temperatur2s of be~ween ~bou~ 200C ~d to about 700C ~ ~s ~o ~hermally degrade the ~mplate or by employing ~me other post-trea~ment process for removal of ~ leas~ part of the template from the TAP~. In ~ome ins~ances the pores ~f the ~APO are ~uff~ciently large ~G
permit tran~port of ~he t~mplate, and, ~c~ordingly, complete or part~l removal ~hcreof ~an be accomplished by conven~on~l desorption procedures such as carr~ed out in ~he case ~f 2eolites~
The TAP0~ ~re preferably formed from a reaction mixtur~ having ~ m~le frac~ion o~ alkali metal ~ti~n which ~s ~ufficiently low th~t it does not ~nterf~r~ with the formation ~ the TAP~
compD~ition. The TAPO com~ositions ~re generally formed ~om ~ r~act~on mixtuge containing re~c~ive ~ources ~f T~O2~ A12~3~ ~nd ~25 organic ~emplat~ng agent, ~aid reaction mixture co~pris~ng ~ composition expr~se~ ln terms of ~olar oxide r~tios ofs ~ R2o-~TixAl~p~1o2-9 ~2 wher~in ~R~ ~ an organi~ ~cmplating ~gen~; hf ~ has v~lue l~rge ~nough to eonsti~u~@ an effe~ive amoun~ of ~R~ ~aid affe~tiYe amount being h~
~mount ~h~ch for~s said TAP0 compositions; "g" has a ~alue ~ r~m zero ~o 500~ ~x~, ~y~ ~nd ~z~
D-139~5 ~ ' ~7~78 - ~2 -represent the mole fractions, respectively of titanium, aluminum and phosphorus in the (TiXAlyPz)O2 constituent, and each has a value of at least 0.001 and being within the quatrilatera~ compositional area defined by points, h, i, j and k which is Fig. 3 of the drawings, said points h, i, j and k representing the following values for nxn ny~ and nzn:
Mole Fraction Point x y z h 0~001 0.989 0.01 i 0.001 0.01 0.989 j 0.32 ~.24 0.44 k 0.98 0.01 0.01 Although the TAPO compositions will form if higher concontrations of alkali metal cation are present, such reaction mixtures are not generally preferred. A reaction mixture, expressed in terms of molar oxide ratios, comprising the following bulk composition is pref~rred:
R2 WM2'(TixAlyPz)2 nH2 wherein ~" is an organic template; "On has a valu~
great enough to constitute an effective concentration of ~R" and is preferably within ~he range-of from greater than zero ~0) ~o abou~ 5.0;
~M" is an alkali m~tal cation ~w~ has a value of from z~ro to 2.5; Wn~ has a value between about zero (0) and about 500; ~x~ ~y~ and ~zw repres~nt the ~ol~ frac~ions, respectively, of ~itanium~ aluminum and phosphorus in ~TiXAlyPz~O2 ~x~, ~y" and wz~ represent ~he mole fractions, re~pectively of titanium~ ~luminum and phosphorus in the ~TiXAlyP~)O~ constituent, and each has ~
value of at least O.U01 and being within the D-13,854 , quatrilateral compositional area defined by points, h, i, j and k which is Fig. 3 of the drawings, ~aid points h, i, j and k representing the following values for "xn, "y~ and ~zw Mole Fraction Point x z_ h 9.001 0.g890.01 o.oal 0.010.9~9 j 0.32 0.2~0.44 k 0.98 0.010.01 When ~he TAPOs are ~ynthesized by this me~hod ~he value of ~mn ~n Formula (1) is generally above about 0.02.
Though the presence of alkali metal cations is not preferred, when they are present in ~he reaction mix~ure i~ is preferred ~o first admix a~
leas~ a portion ~.g. at lea~t abou~. 10 weight percent) o~ each of the aluminum and phosphorus sourc~s in the ~ubstant;al absen~e (e.g. preferably less than about 20 percent of the total weight of the aluminum source and phosphorus source) of the ._titanium sourc~. Thi~ proc:edure avoids adding 'che phosphorus ~ource to za S~asic r~action mix~ur~
containlng the itanium sour~e and aluminum source t ~as was done in mo~t of the publi~hed at~emp~s l:o subst~tute isomorphously 11?021 tetrahedra for ~io;!~ ~e~rahedra in zeoli~ic tructure~3.
Although the r~action mechanis~n is by no means clear ~t thi~ t~m~, the unc~on of the template may be to faYor ~he incorpor~tion of lP02] ~nd [A10;2]
tetrahedra ln the ~ramework ~tructures of the cry~talline products with ~TiOz] tetrahedra isomorphously replacing EPO;~] te~rahedra.
D-13 ,8 54 ~4 .
; 1~
The reaction mixture fr~m which these TAPOs are formed contain on~ or more organic templating agentfi ~templates) which can be m~st any of ~hose heretofore proposed :Eor use in the synthesis of ~luminosilicates and aluminopho~pha~es. The template preferably contains at least one element of Group VA of the Periodic Table, particularly nitrogen, phosphorus, arsenic and/or antimony, more preferably nitrogen or phosphorus and mos~
preferably nitrogen and are of the ~ormula R~X
wherein X i~ ~elec~d from the group ronsisting of nitrogen, phosphorus, arsenic and/or antimony and R
may be hydrogen, alkyl, aryl, araalkyl, or alkylaryl group and is preferably aryl or alkyl containing between 1 ~nd 8 carbon atoms, although more than eight carbon atoms may be present in WR~ of group o the template. Nitrogen-containing templates are preferred, including amines and quaternary ammonium compounds, the latter being represented generally by ~he formula R'4N~ wherein each R' is an alkyl, aryl, alkylaryl, or araalkyl group; wherein R' preferably contains from 1 to 8 carbon atoms or higheE when R' is alkyl and greater than 6 carbon a~oms when Rl i8 oth~rwise t as hereinbefore di~cussed~ Polymeric quaternary ammonium salts ~uch [(Cl~H32N23 tOH)2jX wherein ~x~ has a ~alue of at leas~ 2 ~ay also be employed~ The mo~o-, di- ~nd ~ri~amines, ~ w luding mixed aminest may also be employe~ as templates ei~her alone or in ~ombination with a quaternary ammonium compound or another template~ The exa~t relationship of various template~ when ~oncurren~ly employed i5 no~ ~learly underctood. Mixture~ o~ wo or more templati~g agent~ can produce e~ her mixture~ of TAPOs or in D-13,~54 the instan~e where one template is more strongly directing than another template the more ~trongly directing template may control the course of the hydrothermal crystallization wherein with the o~her template serving primarily to establish the pH
conditisns of the reaction mixture.
Representative template~ include tetramethylammonium, etraethylammonium, tetrapropylammonium or tetrabutylammonium ions;
di n-propylamin~ tripropylamin~; ~riethylamine;
triethanolamine; piperidine; cyclohexylamine;
2-methylpyridine; N~N-dimethylbenzylamine;
die~hylethanolamine; ~icyclohexylamine;
N,N-dimethylethanolamine; 1,4-dia~abicyclo (2,2,2 octane; N-methyldiethanolamine, N-methyl-ethanolamine; N-methylcyclohexylamine; 3-methyl-pyridine; 4~methylpyridine; quinuclidine;
N,N'-dimethyl-1,4-diazab~cyclo (2t2,2) octane ion;
di-n-butylamine, neopentylamine; di-n-pentylamine;
isopropylamine t~bu~ylamine; e~hylenediamin~;
pyrrolidine; and 2-imidazolidone. As will be readily apparent from the illustrativ2 examples ~e~
forth hereinafter, not every ~emplate will produ~e ~very TAP0 composit~on although a ~inyle emplate can, with proper selection of the reaction ~ondi~ions, ~ause ~he forma~ion of different ~PO
compositions, and a ~iven TAPO composition can be produ~ed using diferent template~.
In those instance~ where an aluminum alkoxide is the reac~iYe aluminum ~ource, ~he corresponding alcohol i~ necessarily presen in ~he reaction mix~ure sin~e it ~ a hydrolysis product of the alkoxideO I t has not a~ yet been determined whether ~his alcohol participat~s in the ~yn~hesis D-13,854 '~ff~
~ 16 -process a5 a templatlng agent, or in some other function and, a~cordingly, is not reported as a template in the unit formula of the TAPOs, although such may be acting as templates.
Alkali metal cations if present in the reaction mixture may facilitate the crystallization of certaln TAPO phases, although the exact func~ion of ~uch cations, when present, in crystallization, if an~ not presently known. Alkali cations present in the reaction mixture generally appear in the formed TAPO composi~ion, either as occluded (extraneous) cations and/or as structural cations balancing net negative charges a~ various sites in the crystal lattice~ It should be understood tha~
although the unit formula for the TAPOs does not spe~ifically recite the presence o alkali cations they are not excluded in the same sense that hydrogen ~ations a~d/or hydroxyl groups are not specifically provided for in the traditional formulae for zeolitic aluminosilicates.
Mo~t any reactive titanium source may be employed herein. The preferred reactive titanium sources include ~itanium alkoxidesl water-soluble titanates and titanium chelates.
Most any reactive phosphorous source may be employed. Phosphori~ acid is ~he most sui~able phosphorus source employed ko da~e. Accordingly~
other acids of phosphorus are generally believed to be ~uitable phospho~us sources for use herein.
O~ganic phospha~es such as ~riethyl phosphate have been ~ound ~atisfac~ory, and ~o also have crystalline or amorphous aluminophosphases such as the AlPO~ composi~ions of U.S.P. 4,3109440.
Organo-phosphorus ~ompounds, ~uch as D-13,854 tetra~utyl-phosphonium bromide have not, apparently, served as reactive sources of phosphorus, but these compounds do function as templating agents and may also be capable of being suitable phosphorus sources under proper process conditions (yet to be ascertained). Organic phosphorus compounds, e.g.
esters, are believed to be generally suitable since they can generate acids of phosphorus ln situ.
Co~ventional phosphorus salts, such as sodium metaphosphate, may be used, at least in part as the phosphorus source, but they are not preferred.
Most any reactive aluminum source may be employed herein. The preferred reactive aluminum sources include aluminum alkoxides, such as aluminum isopropoxide, and pseudobeohmite. Crystalline or amorphous aluminophosphates which are a suitable source of phosphorus are, of course, also suitable sources of aluminum. Other sources of aluminum used in zeolite synthesis, such as gibbsite, sodium aluminate and aluminum trichloride, can be employed but are generally not preferred.
Since the e~act nature of the TAPO
molecular sieves o the present invention is not clearly understood at present, although all are believed to contain [TiO2] tetrahedra in the three-dimensional microporous crystal framework structure, it is advantayeous to characterize ~he TAPO molecular sieves by means of their chemical composition. This is due to the low level of titanium present in certain of the instant molecular sieves prepared to date which makes it difficult to ascertain the exact nature of the interaction between titanium, aluminum and phosphorus. ~s a result, although it is believed that titanium, D-13,8~4-C
L7~
l~iO2]~ has substituted isomorphously ~or lAlO2]
or [PQ2] tetrahedra, it is appropriate to characterize certain TAPO compositions by reference to their chemical ~omposition in terms of the m~le ratios of oxides in the as-synthesized and anhydrous ~orm as:
vR . pTiO2 : ~A123 rP2 5 wherein ~R~ represents at leas~ one organic templating agent present in the intracrystalline pore ~y~tem; ~va represent~ ~n effectiv~ amount of the organi~ templat~ng agent to orm said TAPO
compositions and preferably has a value between and in~luding zero and about 3.0; ~p~ 9 ~qW and ~r~
represent moles, respectively; of titanium, alumina and phosphorus pentaoxide, based o~ said moles being ~u~h that hey are within the pen agonal compositional area defined by point A, B, C, D and E
of the ternary diagram which is Fig. 1 of the drawings, said points A, B, C, D and E representing the following values for ~p~, ~q~ and ~r~.
Point ~ 5_ r A . 0~304 1.0 1.22 B 176 lrO 11~0 C 196 1.0 1.0 D 0.828 1.0 0.0143 E . 0O003 1.0 OJ427 The parameters ~p~, ~q~ and "r" are prefera~ly within the pentagonal compositional area defined by points a" b, c, d and e of the ternary diagram which is Fig. 2 of the drawings, said points a, b, c, d and e representing 'che following values for ~Ip~ y ~"
and ~r":
D-13 ~854 Mole Point p q r a 0.008 1.0 1.0 b 1.0 1.0 1.0 c 0.80 1.0 0.60 d 0.333 1.0 0.50 e 0.067 1.0 0.663 The TAPO compositions of this invention have unique surface characteristics making them useful as molecular sieves and as catalyst or as bases for catalysts in a variety of separation, hydrocarbon conversion and oxidative combustion processes. The TAPO composition can be impregnated or otherwise associated with catalytically active metals by the numerous methods known in the art and used, for example, in fabricating catalyst compositions containing alumina or aluminosilicate materials.
TAPO's may be employed for separating molecular species in admixture with molecular species of a different degree of polarity or having different kinetic diameters by con~acting such mixtures with a T~POSs) having pore diameters large enough to adsorb at least one but not all molecular species of the mixture based on the polarity of the adsorbed molecular species and/or its kinetic diameter. When TAPOs are employed for such separation processes the TAPOs are at least partiall~ activated whereby some molecular species selectively enter the intracrystalline pore system thereof.
The hydrocarbon conversion reactions catalyzed by TAPO compositions include cracking, hydrocracking; alkylation of both the aromatic and isoparaffin typ~s; isomerization (including xylene D-13,854-C
,"~, .
.i. c .
~7~
isomerization); polym~rization; reforming;
hydrogenation; dehydrogenation; transalkylation;
dealkylation; and hydration.
When a TAPO containing catalyst composition contains a hydrogenation promoter, such promoter may be platinum, palladium, tungsten, nickel or molybdenum and may be used to treat various petroleum stocks including heavy petroleum residual stocks, cyclic stocks and other hydrocrackable charge stocks. These stocks can be hydrocracked at temperatures in the range of between about 400F and about B25F using molar ratios of hydrogen to hydrocarbon in the range of b~tween about 2 and about 80, pressures between about 10 and about 3500 p.s.i.g., and a liquid hourly space velocity tLHSV) of between about 0.1 and about 20, preferably between about 1.0 and about 10.
TAPO containing catalyst compositions may also be employed in reforming processes in which the hydrocarbon feedstocks contact the catalyst at temperatures between about 700F and about 1000F, hydrogen pressures of between about 100 and about 500 p.s.i.g., LHSV values in the range between about 0.1 and about 10 and hydrogen to hydrocarbon molar ratios in the range between about 1 and about 20, preferably between about 4 and about 12.
Further, TAPO containing catalysts which contain hydrogenation promoters, are also use~ul in hydroisomerization processes wherein the feedstock(s), such as normal paraffins, is converted to saturated branched-chain isomers.
Hydroisomerization processes are typically carried out at a temperature be~ween about 200F and a~out 600F, preferably between about 300F and about D-13,354-C
,4 `
550F with an L~SV value between about 0.2 and about 1Ø Hydrogen is typically supplied to the reactor in admixture with the hydrocarbon feedstock in molar proportions of hydrogen to the feeds~ock of between about 1 and about 5.
TAPO-containin~ compositions similar to those employed for hydrocracking and hydroisomerization may also be employed at between about 650F and about 1000F, preferably between about 850F and about 950F and usually at somewhat lower pressures within the range between about 15 and about 50 p.s.i.g. for the hydroisomerization of normal paraffins. Pre~erably the paraffin feedstock comprises normal paraffins having a carbon number range of C7-C20. The contact time between the feedstock and the TAPO containing catalyst is generally relatively short to avoid undesirable side reactions such as olefin polymerization and paraf~in cracking. LHSV values in the range between about o.l and about 10, preferably between about 1.0 and about 6.0 are suitable.
The low alkali metal content (often not measurable by current analy-tical techniques) o~ the instant TAPO compositions make them particularly ~ell suited for use in the conversion of alkylaromatic compounds, particularly for use in the catalytic disproportionation o~ toluene, xylene, trimethylbenzenes, tetramethylbenzenes and the like. In such disproportio.nation processes it has been obser~ed that isomerization and transalkylation can also oc~ur. The TAPO-containiny catalysts ~or such processes will typically include Group VIII
noble metal adjuvants alone or in conjunction with Group VI-B metals such as tungsten, molybdenum and D-13,~5~-C
chromium which are preferably included in such catalyst compositions in amounts between about 3 and about 15 weight percent of the overall catalyst composition. ~xtraneous hydrogen can, but need not be present in the reaction zone which is maintained at a temperature between about 400 and about 750F, pressures in the range between about 100 and about 2000 p.s.i.g. and LHSV values in the range between about 0.1 and about 15.
TAPO containing catalysts may be employed in catalytic cracking processes wherein such are preferably amployed with feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residues etc. with gasoline being the principal desired product. Temperature conditions are typically between about 850 and about 1100F, LH~V values between about 0.5 and about 10 pressure conditions are between about 0 p.s.i.g. and about 50 p.s.i.g.
TAPO containing catalysts may be employed for dehydrocyclization reactions which employ paraffinic hydrocarbon feedstocks, preferably normal paraffins having more than 6 carbon atoms, to form benzene, xylenes, toluene and the like.
Dehydrocyclization processes are typically carried out using reaction conditions similar to those employed for catalytic cracking. For such processes it is preferred to use a Group VIII non-noble metal cation such as cobalt and nickel in conjunction with the TAPO com~osition.
TAPO containin~ catalysts may be employed in catalytic dealkylation where paraf~inic side chains are cleaved from aromatic nuclei without substantially hydrogenating the ring structure at relatively high temperatures in the range between D-13,854-C
7i~
about 80~F and about 1000F at moderate hydrogen pressures between about 300 and about lO00 p.s.i.g.
with other conditions being similar to those described above for catalytic hydrocracking. TAPO
containing catalysts for catalytic dealkylation are of the same type described above in connection with catalytic dehydrocyclization. Particularly desirable dealkylation reactions contemplated herein include the conversion of methylnaphthalene to naphthalene and toluene and/or xylenes to benzene.
TAPO containing catalysts may be used in catalytic hydrofining wherein the primary objective is to provide for the selective hydrodecomposition of organic sulfur and/or nitrogen compounds without substantially affecting hydrocarbon molecules present therewith. For this purpose it is preferred to employ the same general conditions described above for catalytic h~drocracking. The catalysts are typically of the same general na~ure as described in connection with dehydrocyclization operations. Feeds-tocks commonly employed for catalytic hydroforming include: gasoline fractions;
kerosenes; jet fuel fractions; diesel fractions;
light and heavy gas oils; deasphalted crude oil residua; and the like. The feedstock may contain up to about 5 weight percent of sulfur and up to about 3 weight percent of nitroyen.
TAPO containing catalysts may be employed for isomerization processes under conditions similar to those described above for reforming although isomeriæation processes tend to require somewhat more acidic catalysts than those employed in reforming processes. Olefins are preferably isomerized at temperatures between about 500F and D-13,854-C
- 24 ~
about 9009F, while paraffins, naphthenes and alkyl aromatics are i~omerized at temperatures between about 700F and about 1000F. Particularly desirable isomerization reactions contemplated herein include the conYersion of n-heptane and/~r n~octane t~ l~oheptanes, iso-octanes, butane to iso-butane, methylcyclopentane ~o cylcohexane, meta-xylene and/or ortho-xylene to para-xylene, l-butene to 2-butene and/or isobutene, n-hexene to isohexane, cyclohexane to methylcyclopentene etc.
The preferred ~at~on form i8 a combination of a TAPO
with polyv~lent me~al compounds (such as sulfides) of metal~ of G~oup II A, Group II-B and rare earth metals. For alkylat;on and dealkylation processes TAPO compo~itions haYing pores of a~ least 5A are preferred. When employed for dealkylation of alkyl ~roma~ics, ~he temperature i5 usually at leas~ 350F
and ran~es up to a temperature at which substantial cracking of ~he feedstock or conversion products occurs, generally up to about 700F. The temperature is preferably at leas 450F and not greater than the ~ri~ical temperature of ~he compound undergoing dealkylation. Pressure condi~ions are applied ~o retain a~ least the aromati~ feed in ~he li~uid s~ate. For alkylation ~he ~empera~ure can be ~s low as 250~F but is preferably at least 350Fo In alkylation of benzenet ~oluene and xylene; ~he preferred ~lkylation agents are olefins such as e~hylene and propylene.
The TAPO compositions o this invention may be employed in ~onven~ional molecular sieving processes as here~ofore have been carried out using aluminosilica~e, ~luminophospha~e or other co~monly D-13,8S4 7~7~
- 2~ ~
employed molecular sieves. TAPO composi~ions are preferably activated prior to their use in a molecular sieve process to remove any molecular species which may be present in the ~ntracry~talline pore system as a resul~ of synthesis or otherwise.
For ~he TAPO compositions this is somet;mes accompli~hed by thermally destroying the organic species present in an as-synthesized TAPO since such organic species may be too large to be desorbed by.
convent~onal mean~.
The TAPO compositions of this inve~tion are also use~ul as adsorbents and are capable of ~eparating mixtures of m~lecular speci~s both on the basis of molecular size (kine~ic diameters) and based on the degree of polari y of the molecular ~pel-ies. When the separation of molecular species ~s based upon th~ selec~ive adsorption based on molecular size, the TAPO is chosen in ~iew of the dimensions of its pores such that at least the ~mallest molecular specie of the mixture can enter the intraGry~talline void space while at leas~ the large~t specae i~ excluded. When the separation i based on degree of polarity it is generally the case that the m~re hydrophali~ ~PO will preferen i~lly adsorb ~he more p~lar molecular speGies of a mixture haYing different degrees of pol~rity even though both molecular ~pecie~ ~an communicate with the pore ~ystem of the TAPD.
The instant TAPO compositions may b~
fur~her eharacteri ~ed and dis'cinguished from alu~inoph~s~hate~ by reference to the ca~alytic propertles exhiLbited by th~ TAPO çompos~tions. When the T~PO compositions are tested ~or n- butane crackin~ and compared wit~h aluminophosphate D-13, 854 ~f~7~
- 2~ -compositions having a similar topology it has been observed tba~ the TAPO compositions are more active ~atalysts as indicated by a higher numerical value iEor n-butane cracking. ~rhis comparison will be discussed hereinafter in the examples 38 to 46.
The following examples are provided to exemplify the invention and are not meant to be limiting thereof in any way.
(a) ~xample~ 1 to 20 were carried out to demonstrate the preparation of the TAPO compositions of this invention. The TAPO compositions were ~ar~ied out by hydrothermal crystallization procedure discussed ~upra~ Reaction mixtures were prepared for each exampl~, unless otherwise noted, using titanium source (titanium isoproproxide; 95 wt percent aqueous solu~ion or ~itanium acetyl acetonate (75 wt % in isopropanol)), aluminum ~ource (eithex aluminum lsoproproxide or a pseudo-boehmite phase, 75.1~ wto % A1203 and 24.9 wt % H20), a ~phosphoru~ ssurce ~85% orthophosphoric acid (H3PO~)) t water and at least one organi~
template.
The method of addition of the above mentioned ~omponen 5 to ~he reaction ~ix~ure was done according to three methods ~A, B and C)7 Method~ A, B and C ~re as follows:
METHOD A
The water and aluminum isoproproxide were blended ~o orm a bomogeneous mixture. Phosphoric acid was added to this mixture and blended to form a homogeneous mix~ur~. The t~i~anium sour~e was added to the above mix~ure and the mixture blend~d ~o form D-13,854 .~ . . .
P homogeneous ~ ure,. ~he organic ~emplating agent ~referred to herein a~ ~emplate~ ) wa added ~o thi~
xture and blended un~il 5 ho~ogeneou~ ~xture was observed c METHOD B
The water ~nd phosphori~ ~cid were blended lto ~orn~ a hb~aogeneou~ ~ixture. The p~eudo-boehm~'ce phase was added t~ hi~ mixture ~nd blended ~o form hsmogeneou m~xture. The t~tanium source was ~dded ~o ~his mix~ure until ~ homogeneou~ mixture was obse~ved. ~he s:~rg~nl~ template w~s adde~ to this ~l~sture ~nd blended until a homogeneous mixg:ur~
was obser~e~.
ETHOD C
The water and pseudo-boehmite were blended to form ~ h~mogen~ou~ ~nixtureO ~he t~t~nium sour~e was ~ded . o ~hi~ m~x~ur~ ~nd blended tc~ form a homogeneous mix~ure. Phosphori~ ~cid was ~ddee to this mix'cure and blended t~ provi~e a homogeneDus mix'cure 3fter ~;hi ::h ~he org~nic t~mpl~te w~s ~dded ~nd ~he ~nixture again blended un~il a ho~nog~neous mixture wa~ obs~rvea.
~ 1~) Example~ 1 to 20 w~re ~ar~ied out ~y pr@parlng reae4~on ~ixtur~s a~ ~bo~ ~e~rib~d, using the amount~ ~t ~or~h in ~ble I~
t~ h@ c~mpos~ n ~ ~h~
~iactur~ of l~xample~ 1 to 20 wer~ ~xpr~ssed in terms o th~ ~ol~r ga~clo o ox~ 1$ fQllOW~
~ sA~203: J?25~Ti~28 ~ ~2 wh~r~n ~R" i~ templ~'cs pr~s~n~ in amoun~ nd 18 the mol~r r~tlo o template t~ mole ~f ~2~
~nd ~ gh~ a~ 2 ~o A1203. q~he ~ cte~ t~flplDte and th~ value~ f~3r n~l w~ ~re ~ o~ bl~
D-13 ~oB541 . ~ . . . . . .
~z~
(d) The reaction mixtures were then each sealed in a stainless steel pressure vessel lined with polytetrafluoroethylene and heated in an oven at a temperature (see Table II) and for a time (see Table II) at the autogeneous pressure. The solid reaction product was recovered by filtration, washed with water and dried at room temperature.
(e) The products obtained in part (d) for Examples 1 to 20 were analyzed by X-ray powder diffraction and characterized to be the TAPO
compositions set forth in Table II.
(f) The X-ray patterns carried out herein and all Gther X-ray patterns appearing herein were obtained using standard x-ray powder diffraction techniques. The radiation source was a high-intensity, copper target, X-ray tube operated at 50 Kv and 40 ma. The diffraction pattern from the copper K radiation and graphite monochromator is suitably recorded by an X-ray spectrometer scintillation counter, pulse height analyzer and strip chart recorder. Flat compressed powder samples are scanned at 2(2 theta) per minute, using a two second time constant. Interplanar spacings (d) in Angstrom units are obtained from the position of the diffraction peaks expressed as 20 (theta) where theta is the Bragg angle as observed on the strip chart. Intensities were determined from the heights of diffraction peaks after subtracting background, IIIol' being the intensity of the strongest line or peak, and "I" being the intensity of each of the other peaks. ~hen Relative Intensities are reported the following abbreviations mean: vs = very strong; s = strong; m = medium, w =
weak; and vw = very weak. Other abbreviations include: sh = shoulder and br = broad.
D-13,854-C
a - 2g As will be understood by those skilled in the art the determination of the parameter 2 theta is subject to bo~h human and mechanical error, which in combination, can impo~e an uncertainty of about l0.4 on each repor~ed value of 2 theta. This ~uncertainty is, of course, also manifested in the reported values of the d-spacinys, which are calculated from the 2 theta valuPs~ This imprecision is general throughout the art and is not ufficient to preclude the differentiation of the present ~ryætalline ma~erials from each o~her and ~rom the compositions of the prior art.
D-13~854 ~ ~2~ ~
o c m m ~ m m m a~~ m m ~ ct m m m m m ~ E
OIl~ I~ oc~ IY~ ~) ~ ~ CO _ N ~ co oo cr~ O~ O ~t ~t ~ ~ E
O a) 3 ~ D a~ ~ ~ tv~ ~ ~ ~ ~ ~ _ ~ ~ _ ,, _ _ _ _ -- -- -- ,,, :
E
V ~ ~ I~ O O O ~ ~ ~
T ~
m ~r x ,_ 1~ ~ C ~ c u v ~ ~
,_ E ,_ Q
E c r~ ~
~t2 ~ r G ~ ~ q ~ ~ ~ ~r ~ ~ ~ ~ ~ ~ ql ,~, , c o _ ~ ~ o ~ U
o 1- a L ~ N ~J N N ~ ~ N ~ G u ~ x "~
O . _ ~ L L
.:t .~, ~ O tll X CL ._ ._ L ~ E
* -- ~r) -- ~ ~ ~; ~ o o o 1~ 1~ 1~ 1~ 1~ ~ c; o ~o O ~ ~ L ~ '~ ~ ._ U
a~ c ~
> , ~ ~ E
2 I T T T I I T _ _ _ T 2 T I I I ~ ~ 2 L L ~ ~
~ ~ e ~ ~o <3C o <ot L L L ~0 0 ~ ~0 ~0 0 L L O ~ 1~ C E E
E ~ C C C 1~ t C C 1-- O ,, ~_ ~ V C
E X 1~ _ _ al LO ~ ~ ~1) _ ~J 1 1 ~ U'l ~D r~ ~ ~ o _ t~l ~ ~ 11'1 ~O 1~ ~ ~` n~ 1-- s i-- 1-- 3 ~ _ . _ _ _ _ ~ ~ ~
X _ ~
~J
.., ,..,, . ~
_ , ., , o g o ~:
L O O O O O O O O O O O O O O O O O O O O ~ ~
o ~r <r a ~ ~ ~ ~ ~ ~ ~ ~ ~ ~, c L ~
s E ,~_ E ^ o, S ~ ~ O O O ~ O q` O ~ O O ~ O O O ~r c Q L V~
E N ~ \1 E L ~ ~ _ C Q Q
O O O O O O O O O O O O O O O O O O O O ~ T IIS 4~
EIr~ O Ll-) O 11~ 0 U') O 10 0 0 Lrl In 11~ Lr) O Ll ) O 1~ 0 (D Z
I_ N -- N ~ N -- N -- N ~ -- -- _ N -- N -- ~J ~ L ~
~¦ C~ L a ~¦ ~ N ~ ~) ~ D ~ ~ ~) ~1 'D '.D r~ ~ ~O ~J ~ ~ Q C
~> OO--C;OOOOOOOOOOOOOOOO
O O I aJ
O O ~ Q
E ~ c ~> 2 2 2 T I O ~ v) C ~
r- 2 2 I I T I ~: 2 -- ^ ^ I T I I I I ~ ~ T Q E ~11 <D O
Q ~ 3 ~ ~ 3 ~ ' ~ ~ ~ ~ L L aJ q~
1~ 1~ 1- 1- C C C 1-- 1- ~ 1- 1- 1~ C C 1-- Q ~ Q
~ T L C~ L
~ ~ ~ a X nE~
E -- ~ tY ~t If) ~ I` C!~ cn o -- N l'') ~ Il') D 1~ CO a~- O
3 N _ N
~2~7~
ra) The products of examples 8, 10, 13 and lB were calcined at 600C~ 550C and 600C and 550C
in air for 1.5, 1.0, 105 and 1DO hour~, re~pecti~ely. The ~APO'~ were then employed to determine adsorption capacities of TAPO-5, TAPO-ll, TAPO-13 ~nd TAPO-31~ respectively~ as prepared in these examplesO The adsorption capacities were measured using a ~tandard McBain-Bakr gravimet~ir adsorpt~on apparatus on ~amples activated in a vacuum at 350~C.
The data for TAPO 5, T~PO-ll~ TAP0-18 and TAP~-31 were as ~11OWS ~nd as ~e~ forth in (b), ~c~, (d) and ~e), hereinater.
(b) TAPO~5:
Kinetic Pr2ssure Temp. wt ~
Diameterj A~ (Torr) (~C) Adsorbed 2 3.46 101 ~lB3 10~6 2 3.46 736 ~183 16.1 Cyclohexane 6~0 4~ 22.9 10.5 Cy~loh~xane h~0 67 22.9 18~6 ~2 2.65 11 22.~ 19.1 ~2 2~65 1~ ~2.~ ~8.3 D-13~54 (c) ~AP0 ~
Kinetic Pressure Temp. wt ~6 Diameter~ A (TorrL ~C) Ad~orbed Q2 3~46 101 lB3 6.7
5)2 3.~6 736 183 9.
Cyclohexane 6 ~ 0 12 22 . 9 3 .. 5 CyClQheXane 600 67 2209 8~5 Neopen~ane 6 0 2 101 P.mb~ 1. O * *
Neopentane 6.2 742 ~mb* 2.8***
H20 20~5 11 22.4 14.5 H 0 2.65 19 22~5 18.7 .
__ * ~mb ~ ambient temperature *~ weigh~ % absorbed after 3 hours *** weight % abst~rbed after 5.5 hours (d ) TAP0- 18 .
.
~Po-la l~ineticPressur~Temp. w~ %
Ad~orbed 3 46 101 -îB3 24.0 3,q~ 739 183 29.7 n-Hexene 403 101 2490 19- 1 ~so~butane 5.0 103 24.5 0.68 Iso-butane 5~0 7~2 24.4 2.0 0 2~65 11 ~4.4 35.7 ~2~ 2~5 lg ~4.3 38"2 D-13, ~54 -~2~7~
(e3 T~P0~31:
TAP0 ~ 31 Rinetic Pressure Temp. wt ~
Diame'cer, A (Torr3 (C~- Adsorbed 2 3.. ~6 101 -183 7 2 3.46 736 183 10.4 Cyclohexane 6 . 0 12 22 . 9 4 . 9 Cy~lohexane 6.0 67 22.9 9.4 Neopentane 6 . 2 101Amb* 3 . 9* *
Neopentane 6 .,~ 742Am~* 7. 0*~*
~20 2.65 11 2~.41306 EI20 2.65 19 22.51805 .
-* Amb - ambient temperature k* weight % adsorbed at 3 hours *** weigh'c % adsorbed a~ 5,. 5 hours (f) From the data se~ f~rth in parts (b), (c~, (d) and (e) it was determined ~ha the p~r~ ~ize e~f TAP0~5, TApo~ll 9 TAP0-18 and TAP0-31 were as follows:
1) TAP0~5; grea~er ~han about 6. 2~;
2) TAI?0~ about 6. 0A;
3~ TA~0-18: about 4. 3AQ, and - 4) TAP0-31s greater ~ban about 6.2~
EXAMP LES ~2 2 - 3 0 (a) Th~ as-~ynthesi~ed products of Exampl~ 9, lOt 11" 13, 15, 16, 19 and 20 w~re analyzed (chemical analysis~ ~o d~termine the weight percen~ A12~3, P;~05, Tio2, LOI ~Loss on Ign~tion) and the ratio of carbon to nitrogen ~-13 ~ 854 - ~Z~71~8 .pre~en~ re~ult of ~h~ ~empl~teO Th~ r~ults of thes~ analyses ~r~ set ~srth, ~elow~ ln Tnble ~II
~ABL~ III
Ex~tnple gample ~1203. P205TiO~ LOI /~t ~2 læx, 1 3~.7 46.4 1.3 14"~12 23 ~x. 9 36.3 4~,.7 ~,7 10.~ 9 24 E:x. 10 36.3 ~19.5 20~ 10.
~. 11 3~07 5û.0 1,.2 11.9 2~ ~x. ~3 40.5 36.9 1.38 19. 1 27 ~ . 15 3503 4~.2 ~.23 2~ x. 1~ 340~ ~03 ~.57 1709 2~ ~3x~ 19 3609 ~503 2.5 13~3 6 ~x. 20 34.1 ~1500 O.lB 19~4 4 ...........
_ .
1 ex~mple ln whi~h the ~ample was pr~p~red 2 weight r~tlo of ~rbon to nitrogen ~ b) ~D~X (eneryy ~ sper~ive analy~is by x rz~y~ ~icroprobe ~nalysis was c~rried ou~ on ~lean crystals (polished w~th diamon~ powder and carbon coat~d) ~n the product prep~red ~n ~xample 3, ~upr~. ~e ~D~X mi~roprobe analyRi ~showed .hst 006 weight perc~nt ~it~nium w~s pr~gent ~s ~n integr~
p~rt ~f the ~ry~tal part~ele o~ 'che T~PO
compos~Lt~n~ ~he r~laS:lve a~nount~ of P2l3~j,9 A1203, and ~iO2~ normali~:~a t~ lûO p~rcenS
~ ed on P;~Q5~ ~1203 ~nd ~~ d ; ~xpre~2a ~ we~ght pær¢~nt were ~25 ~7 a~l2o3 ~.6 g!~o2 ~- ~7 EDP.X ~ ropEob~ y~iR wa~ c~r~d out the pro~3u~t~; o ~xampl~ 10 ~n~l 15 but the ~e~ult~
~r~ eonclus~Ye ~wirlg ~eo the $rn~ @ of the ~3,~S~
., ~ ,.~
~ ~7~78 crystals employed for analysi~ and possibly the amount of titanium present.
(c) ED~X (energy dispersive analysis by-x-ray) microprobe analysis was carried out on TAPO crystals prepared in examples 1 ~nd 10, ~upra.
The EDAX microprobe analysis is set forth in the ~ollowing table. With relative amounts of TiO2, normalized to 100 percent based on P2O5, A12O3 and TiO2 and expressed as a weight percent being as follows:
TAPO ~ TiO2 TAPO-5 1 ~ 2 TAPO-ll 10 ~ 1 to 2 Several other TAPO compositions were analyzed by the use of EDAX but ~hese analyses were not definitive due ~o the crys~l size requirement and/or de~ectio~ limits of EDAX.
t~ TAPO-5, as referred to in example 39 was subje~ted to x-ray analysis. ~APO-5 was de~ermined to have a characteristic x-ray powder diffrac~ion pat~ern which contains at leas~ the d-~pacing set forth in Table V below:
TABL~ V
~ 2~ d,~A~ .Relative Intensity 7.5 11.7~ v 15.0 5.91 m 19,.9 ~io46 m 21.0 . 4.23 m 22.~ 3.95 2~.2 3O~0~ .
D-13,854 3-z~ 7~3 . .
,~ -- 37 ~
The ~s-~yrlthe~z~d TAP0-S composi~on~ Por wh~ch x-Yay powder diffr~ction data have ~een obtainea, including the TAP0 characterized by Table V, So da~e have patt@rn8 wh~Gh are char~c~erized by lthe ~ata of ~Pablq~ V~ belowo.
~!~2LE VI
2~ dJ ~A~ lOa x I/I 0 . _ _ __ 7., 5 1:1 ~7~ 100 907* 9.12 13 .0 ~ ID Bl 11 15.0 5.91 2~
19 G 9 ~l o~6 ~15 21~0 4~23 56 21~ 08 22~5 3~95 89 24~8 3~59 12 2S.4 ~sh3 ~3.507 ~6.2 3.401 32 ~9.0 3.079 18 30.2 2~59 19 3307 2.660 6 34~ i!o578 16 3~2 2.41'~ 5 37~1B 2 .3B0 14 41.8 2.161 3 4206 ~ 2 3 480~ 95 .
sh ~ shoulaer peak Taay contaln ~n lmpurity (b) ~ por~on of ~he ~ yn~hesized TAP0~5 sf p~!l2~: gl) W~S caï~ d ~n ~lr at 600~C for ~bout i.5 hour~. ~h~ calc~ne~ pr~auc~ was t:) ~rac~Eiz~d ~y ~he ac~y powd@r ~l~f~c'cion p~tterrl o~ ~bl~
~elow:
a~13~ ~4 ., .
,: :
., ~, , ~
~Z~ 7~
~ABLE A
2a d, (A)Relative Intensity 7,.4 llog5 vs 12.9 6.8~ w 19 . 7 4 . 51 m 210 2 4 .19 m ~2.4 30~7 s 25.9 3.440 m ~ he cal~ined T~PO-5 cvmpositions for which x-ray powd~r diffraction data ~ave been obtained ~o date have patterns which are characterized by the x ray powder diffrac ion pattern shown in Table B, below:
TAELE B
2~ d, ~A) 100 x I/I O
7.4 11.95 100 12~,9 6.~6 17 1~,,9 5.g5 7 19.7 4 ~ ~127 21.2 4. 19 39 210~* ~1,.08 8 22~4 3~97 7a 24 ~ 3~5~1 9 - 25 9 3.4'1025 2!3o~ 3~7~ 13 3t~0 2~197813 33~7 ~2~660 4 34~5 ~6~)0 9 3 ~ 4 3 1~ 4 37~8 2~31~ 10 42~3 ;2~137~2 ~3~1 2~)99 2 47~7 105il07q * peak may contain an impurl'cy D-13 ,854 7~
EXAMP~E 32 (a) TAPO-ll, as referred to in example 10, was subjected to xray analysisO
TAPO-ll was determined to have a ~haracteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table VII, below:
TABLE VII
2~ d,~A) Relative Intensi~y 9.5 9~31 m 20.5 4.33 m 2~.9 ~.~S vs 2~2 4.00 s .
~2~5 3.93 s 23.2 3.83 s All of the a~-synthesized TAPO-ll ~ompositions for which x-ray powder diffrac~ion data have been obtained t4 date have patterns which are characterized by ~he data of Table VI~I, below:
2~ d,(A) 100 x I/I O
~1 10~92 3~; -9 o 59 D 31 5~i 13 o ~ 71 17 1~7 5~;4 32 1603 5~44 5 19.0 d~67 7 20~5 4033 52 20~9 D.~25 100 22~2 4~0Q 67 22~6 3~93 73 ;23~2 3.1~3 74 2408 3~5~ I 5 2~o~ 3~376 17 26~6 3~3~;1 19 D~13,854 ~z TABLE VIII ~Continued) 2~ d, (A) 100x I/I 0 28.~ 3.143 --28 . 7 3 . 110 18 29.1 30069 8 29~5 2.52B 10 31,5 2.~40 12 33.0 2.714 19 34 .3 2,. 614 11 3~. 7 2 . 515 6 36~6 2.,456 7 37.~ 2.392 1~
37~8 2.381~ 16 39.3 2.29~ 4 ~2 .2 2. 141 4 42 . B 2.113 5 4500 2. ~14 6 46.0 1.973 3 47.1 1.92g 3 4~1 1.892 3 4B.9 1.863 5 50.8 1.797 6 5~.8 1.675 (b3 A portion of the assynthesized TAP0-11 of part a) was calcined in air at 550C for 1.5 hours. The calcined product was characterized by the x-ray powder dif fraction pa'ctern of Table C, below:
TABL}: C
2~ d~ (A) 100 x I/I O
__ 9.8 9.03 m :L601 5. 51 n~
~1.9 4006 vs 22.4 3.97 m 23,5 3,.79 m 29~7 3Oal08 m D-13 ,854 ~7~
~1 -All of the ~alcined TAPO-ll compositions for which x ray powder diffraction data have been obtained to date have patterns which are ~haracterized by the data of Table D, below:
TABLE V
29 d t (A) 100 x I/I O
8~ 1 10~ 92 22 9~8 9~03 J,2 L~7 7~S6 7 12~8 6~92 22 13 ~ 7 6 r 4 6 9 14.~i 6~07 6 16~ 1 5 ~ 51 54 ~, 170~ 5~07 6 19.5 (sh)4.55 19 1909 ~.~6 25 20.8 4.27 12 21.9 4.0~ 100 22.4 (sh)3.g7 54 23.~ 3.79 57 2400 3.71 20 2403 (sh)3.66 17 25~8 ~.453 24 26.7 3.339 16 27.2 3.278 ~8 27.~ 3.209 22 28.6 3.~21 10 29.7 3.~8 32 30.4 2.94~ 19 31.8 ~.~14 12 32.6 2.755 34~0 2.637 12 34 ~ 5 2 a 600 7 35~6 ;~5~!2 14 37.2 2.417 11 38.2 (sh~2.356 6 38.6 2.33~ lS
41~0 2~201 1 ~3.6 2.07 4~ 2.~3~ ~
45.2 2.006 4 49.1 1.85~ 11 ~9.6 1~38 . 10 50~4 lo Bll 4 52~ 746 d~
53~7 1.71~7 5 7 1~678 4 ~-13~B54 .
7~f~
~ ~2 -a) TAP0-18, as referred to in example 15, was subjected to x-ray analysis. TAP0-18 was de ermined to have a characteristic x-ray pswder diffraction pattern which contains at least ~he d-spacings set ~orth in Tabl~ IX below:
T~BLE IX
d,(A)Relative Intensity ,.
~ . 643 9 . 17 vs 16.87g 5025 m 170961 5.20 m 22.227 4.00 m 25 . 3 54 3 . 513 m 25.462 3,.498 m 26.~85 341 s b~ ~11 o the as-synthesized TAP0-18 compositions ~or which X-ray powder diffraction da'ca have been obtained to date have patterns which are characterized by the data of Table X, below:
TABLB X
d, (A)100 x I/I ,~
__ g ~643 9 o 1~ 10~) 10~474 8~15 3 :IL1.t~35 g~2 5 :~L3.1!~3 ~6~71 2 lq.~)55 6~30 3 14~E~34 5~97 3 15~55~ io70 12 ~L~o879 5~25 28 17~ 5~2~ 29 17~. 943 4 ~ 514 ~!0 18.!31~;7* 4~6~3 12 19~3 4~6 1~o556 4~3 2 20~ 210 4 ~ 3 9 2 20~729 4~29 3 D~13 D~54 ~L2~7~
~ 43 --TABLE X (Continued~
d, ~A)100 x I/I O
-21.0~10 4.22 22 22.227 4.~0 27 23.404 3.80 3 23.978 3.71 4 24.478 3.64 7 24.,6 ~h) 3~,62 --25000~ 3.5~2 11 25.3~1* 3.513 34 25.4~2 3.~8 32 ~6.173 3~401 6 26.685 3.340 60 2?.4 3.,26û
28.1D~9 3.17~ 15 2~.327 3.045 30,135 20966 13 30.877 2.896 5 31.428 2.8~6 9 31.~99 2.~05 32.525 20753 17 33.542 2.672 3 34 ~4 Sl 2 o603 2 34O547* 2~596 2 3 6 ~ 10 0 2 ~ 8 ~3 37~833 2~378 3 38,051 2.3~5 2 38.35~ 2.347 2 38.501 2.338 2 39.9 ~t.26 41 ~890 2 ~ 157 3 ~3~123 2~09~3 3 43~6 2.t)~10 ~5.3~12* 2~0t~0 6 46.795* 1~,941 B
~7.372~ ~.91~ ~
~708~7 ~.899 6 4 8 . 731* l o B 67 15 49.67~ 35 6 ~O.û5~ 22 2 5~ ,. 159 1.785 2 52.11~1 1.755 2 5~.0~1 1c696 2 54.2~9 1.691 2 54.671 1.,678 3 55.260 1.662 3 *peak may c~n~aI;~b~jCrity 8h c shoulder 3 ,~5~
, ~2~ 7 ~ ) ~APO-lB, as referred to in example 15, was subjected to X-ray analysis after calcination at 550C in air for 1 hour. T~PO-18 was determined to have a characteris'cic X-ray powder diffraction pattern which contains at least the d-spacing set forth in Table E, below:
TABLE E
2~ d, ~elatiYe Intensi~cy 9 . ~ 9 . 31 ~s 9-~ ~.21 YS
21.8 4.0~ m 22.9 3~88 w 29.0 3.079 m 31.0 2~,885 m b) ~11 of ~he ~alciried TAPO-18 compositions for whach X-ray powder diffraction data have been obtained to date have patterns which are charac'cerized by the data of Table F, below:
TAB
2~ d, (A) 150 x I/I O
___ 9~5 g.31 97 9~ 6 9 ~ 21 lt~t~
10.~; 8035 10 11~2 7 o 90 1~
13~4 ~161 113 14~4 6~ lS 10 16.0 5~5~1 13 L6~5 5~37 5 1~ ~ 1 5 ~ 1~ 18 1804 4~82 ~;
l9oO ~1.67 7 19,.5 ~a~s5 3 20~7 4~o29 13 D 13 ,854 ~73L~
TABLE F (Continued~
d,(A~ 100 x I/I O
21.8 4.08 46 22.9 3.88 15 24.2 3.68 11 24.7 3.60 10 25.5 3.493 8 26.2 3.401 7 27.1 3.290 1~
27.5 (sh~ 3.243 --28.2 3.164 5 29.0 3.~79 21 ~9.4 3.038 10 29~8 2.998 10 31.0 2.885 23 31.5 2.840 12 31.9 2.805 7 32.4 2.763 6 33.1 2.706 8 33.7 2.660 11 34.6 2.592 5 35.5 2.529 6 36.9 2.436 6 3~.9 2.315 5 42.7 2.118 44.7 2.027 3 46.8 1.941 2 47.8 1.903 4 49.3 1.848 2 49.7 1.834 3 51.8 1.765 4 54.0 1.698 3 a~ TAPO-20, as referred to in example 17, was subjected to X-ray analysis. T~PO-20 was determined to have a characteristic X-ray powder diffraction pattern which contains at least the d-spacings se~ forth in Table XI, below:
D-13,854-C
3 r~
~i TAELE XI
2a d, lA)Relative Intensity 14.0 6.33 m 19.8 4.48 m 24.~ 3.65 vs 23.2 3.164 m 31.6 2.831 w 34~6 2.~ w All of the as-~ynthe~ized TAP0-20 composit~ons for which X~ray powd~r difractiorl data have been ob~ained ~o da'ce have pa~terns which are characterized by the data of Table XII, below.
.
TABLE X I I
2~ d, (i~lOa x I/I O
14.0 6.33 52 19.8 4.4~ 46 21.3* ~a.17 2 21~9* ~.06 2203 3~g9 ~
22.5 (~h) 3.95 --23.0* 3.87 2 24~ 3.65 100 28.2 30164 21 31.5 20~31 12 3406 ~.592 17 37.,~ 2.3g2 --38.~* 27344 2 40.2 2420,3 ~2.9 2.108 5 ~7. ~ 1 . 903 2 52.2 1.752 12 . ~ .
~h - shoulder * peak may ~ontain an impuri'cy b~ A por~ on of the as-~ynthesiz~d T~ 20 o~ part a) was calcined in air at 550~C ~or D-13, 854 .~
~2~
1.0 hour. The calcined product was characterized by the X-ray powder diffraction pattern containing at least the d-spacing of Table G, below:
TABLE G
d,(A)Relative Intensity 14.3 6.19 vs 20.2 4~40 w 24.6 3.62 m 2~.5 3.132 w 31.8 2.~14 vm 35.0 2.564 w All the calcined TAPO-20 compositions for which X-ray powder diffraction data have been obtained to date have patterns which are characterized by the X-ray powder diffraction pattern of Table H, below:
TABLE H
d,(A)100 x I/I O
14.3 6.19 100 20.2 4.40 15 22.5 3.95 5 24.6 3.62 48 28.5 3.132 11 31.8 2.~14 9 35.0 2.564 10 37.9 2.374 40.7 2.217 2 43.2 ~.100 2 48.2 1.888 2 5~.6 1.740 6 a) TAPO-31, as referred to in example 18, was subjected to X-ray analysis. TAPO-31 was D-13,854-C
. . .
~7~7~
determined to have a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIII, below:
TABLE XIII
20 d,(A)Relative Intensity 8.510.40 m 20.9 4.25 s 21.~ 4.19 s 22.5 3.95 vs 22.7 3.92 vs All of the as-synthesi2ed TAPO-31 compositions for which X-ray powder diffraction data have been obtained to date have patterns which are characterized by the data of Table XIV, below:
TABLE XIV
20 d,(A~100 x I/I O
7.012.63 21 8.510.40 56 9.6 g.21 2~
9.8 (sh) 9.03 --11.8*7.50 10 13.3 6.56 9 13.8 6.42 13 14.8 5.99 4 15.8 5.~1 7 17.0 5.22 4 18.4 4.8~ 8 19.1 4.65 5 20.2 (sh) 4.40 --20.4 4.35 48 20.~*4.25 60 21.2 4.19 68 22.0 4.04 43 22.5*3.95 9~
22.7 3.92 100 23.3 (sh) 3.82 35 24.6 (sh) 3.62 _._ D-13,854-C
., ~
~ ~ ~' t ,. . .
~h~7~
~ g TABLE X~V ~ContinuedL
2B d, IA)lOC x I/I 0 25.4 305~7 16 2603 ( h) * 3.389 --26.5* 30363 50 26.7 (sh) ~ 3.339 --27.8 3.209 ~3 2~. 2 3 . 1~4 --28.B* 3.100 8 2~.6 3~ 6 30.0 ~.97g 5 31.5~ 2~B40 14 33.0 - 2.714 5 33.6 2.6Ç7 S
35.1 2.557 7 35.9 2.501 8 37.B 2.380 13 40.0 20254 7 ~2.2 2.141 16 49.7 1.834 12 -~h - ~houlder * peak may contain an impurity b) ~ portion of the as-synthesized TAP0-31 of part a) was calcined in air at 550C for 1.0 hour~. The calcin~d product was characterized by the X-ray powder diffraction pattern of Table M, below:
. TA3LE 11 d, ~A3Rela~ive Intensity 8.5~ 4~ YS
9.8 9.03 w 20~3 4.37 m . 0 2 .6 . 3.93 vs 31~7 2.823 m D-13 ,854 . ~
7~
All the calcined TAPO-31 compositions ror which X-ray powder diffraction da~a have been ohtained to date have patterns which are haracterized by the data of Table N, below:
TABLE ~
d,(A)100 x I/I O
5.8* 15.24 3
Cyclohexane 6 ~ 0 12 22 . 9 3 .. 5 CyClQheXane 600 67 2209 8~5 Neopen~ane 6 0 2 101 P.mb~ 1. O * *
Neopentane 6.2 742 ~mb* 2.8***
H20 20~5 11 22.4 14.5 H 0 2.65 19 22~5 18.7 .
__ * ~mb ~ ambient temperature *~ weigh~ % absorbed after 3 hours *** weight % abst~rbed after 5.5 hours (d ) TAP0- 18 .
.
~Po-la l~ineticPressur~Temp. w~ %
Ad~orbed 3 46 101 -îB3 24.0 3,q~ 739 183 29.7 n-Hexene 403 101 2490 19- 1 ~so~butane 5.0 103 24.5 0.68 Iso-butane 5~0 7~2 24.4 2.0 0 2~65 11 ~4.4 35.7 ~2~ 2~5 lg ~4.3 38"2 D-13, ~54 -~2~7~
(e3 T~P0~31:
TAP0 ~ 31 Rinetic Pressure Temp. wt ~
Diame'cer, A (Torr3 (C~- Adsorbed 2 3.. ~6 101 -183 7 2 3.46 736 183 10.4 Cyclohexane 6 . 0 12 22 . 9 4 . 9 Cy~lohexane 6.0 67 22.9 9.4 Neopentane 6 . 2 101Amb* 3 . 9* *
Neopentane 6 .,~ 742Am~* 7. 0*~*
~20 2.65 11 2~.41306 EI20 2.65 19 22.51805 .
-* Amb - ambient temperature k* weight % adsorbed at 3 hours *** weigh'c % adsorbed a~ 5,. 5 hours (f) From the data se~ f~rth in parts (b), (c~, (d) and (e) it was determined ~ha the p~r~ ~ize e~f TAP0~5, TApo~ll 9 TAP0-18 and TAP0-31 were as follows:
1) TAP0~5; grea~er ~han about 6. 2~;
2) TAI?0~ about 6. 0A;
3~ TA~0-18: about 4. 3AQ, and - 4) TAP0-31s greater ~ban about 6.2~
EXAMP LES ~2 2 - 3 0 (a) Th~ as-~ynthesi~ed products of Exampl~ 9, lOt 11" 13, 15, 16, 19 and 20 w~re analyzed (chemical analysis~ ~o d~termine the weight percen~ A12~3, P;~05, Tio2, LOI ~Loss on Ign~tion) and the ratio of carbon to nitrogen ~-13 ~ 854 - ~Z~71~8 .pre~en~ re~ult of ~h~ ~empl~teO Th~ r~ults of thes~ analyses ~r~ set ~srth, ~elow~ ln Tnble ~II
~ABL~ III
Ex~tnple gample ~1203. P205TiO~ LOI /~t ~2 læx, 1 3~.7 46.4 1.3 14"~12 23 ~x. 9 36.3 4~,.7 ~,7 10.~ 9 24 E:x. 10 36.3 ~19.5 20~ 10.
~. 11 3~07 5û.0 1,.2 11.9 2~ ~x. ~3 40.5 36.9 1.38 19. 1 27 ~ . 15 3503 4~.2 ~.23 2~ x. 1~ 340~ ~03 ~.57 1709 2~ ~3x~ 19 3609 ~503 2.5 13~3 6 ~x. 20 34.1 ~1500 O.lB 19~4 4 ...........
_ .
1 ex~mple ln whi~h the ~ample was pr~p~red 2 weight r~tlo of ~rbon to nitrogen ~ b) ~D~X (eneryy ~ sper~ive analy~is by x rz~y~ ~icroprobe ~nalysis was c~rried ou~ on ~lean crystals (polished w~th diamon~ powder and carbon coat~d) ~n the product prep~red ~n ~xample 3, ~upr~. ~e ~D~X mi~roprobe analyRi ~showed .hst 006 weight perc~nt ~it~nium w~s pr~gent ~s ~n integr~
p~rt ~f the ~ry~tal part~ele o~ 'che T~PO
compos~Lt~n~ ~he r~laS:lve a~nount~ of P2l3~j,9 A1203, and ~iO2~ normali~:~a t~ lûO p~rcenS
~ ed on P;~Q5~ ~1203 ~nd ~~ d ; ~xpre~2a ~ we~ght pær¢~nt were ~25 ~7 a~l2o3 ~.6 g!~o2 ~- ~7 EDP.X ~ ropEob~ y~iR wa~ c~r~d out the pro~3u~t~; o ~xampl~ 10 ~n~l 15 but the ~e~ult~
~r~ eonclus~Ye ~wirlg ~eo the $rn~ @ of the ~3,~S~
., ~ ,.~
~ ~7~78 crystals employed for analysi~ and possibly the amount of titanium present.
(c) ED~X (energy dispersive analysis by-x-ray) microprobe analysis was carried out on TAPO crystals prepared in examples 1 ~nd 10, ~upra.
The EDAX microprobe analysis is set forth in the ~ollowing table. With relative amounts of TiO2, normalized to 100 percent based on P2O5, A12O3 and TiO2 and expressed as a weight percent being as follows:
TAPO ~ TiO2 TAPO-5 1 ~ 2 TAPO-ll 10 ~ 1 to 2 Several other TAPO compositions were analyzed by the use of EDAX but ~hese analyses were not definitive due ~o the crys~l size requirement and/or de~ectio~ limits of EDAX.
t~ TAPO-5, as referred to in example 39 was subje~ted to x-ray analysis. ~APO-5 was de~ermined to have a characteristic x-ray powder diffrac~ion pat~ern which contains at leas~ the d-~pacing set forth in Table V below:
TABL~ V
~ 2~ d,~A~ .Relative Intensity 7.5 11.7~ v 15.0 5.91 m 19,.9 ~io46 m 21.0 . 4.23 m 22.~ 3.95 2~.2 3O~0~ .
D-13,854 3-z~ 7~3 . .
,~ -- 37 ~
The ~s-~yrlthe~z~d TAP0-S composi~on~ Por wh~ch x-Yay powder diffr~ction data have ~een obtainea, including the TAP0 characterized by Table V, So da~e have patt@rn8 wh~Gh are char~c~erized by lthe ~ata of ~Pablq~ V~ belowo.
~!~2LE VI
2~ dJ ~A~ lOa x I/I 0 . _ _ __ 7., 5 1:1 ~7~ 100 907* 9.12 13 .0 ~ ID Bl 11 15.0 5.91 2~
19 G 9 ~l o~6 ~15 21~0 4~23 56 21~ 08 22~5 3~95 89 24~8 3~59 12 2S.4 ~sh3 ~3.507 ~6.2 3.401 32 ~9.0 3.079 18 30.2 2~59 19 3307 2.660 6 34~ i!o578 16 3~2 2.41'~ 5 37~1B 2 .3B0 14 41.8 2.161 3 4206 ~ 2 3 480~ 95 .
sh ~ shoulaer peak Taay contaln ~n lmpurity (b) ~ por~on of ~he ~ yn~hesized TAP0~5 sf p~!l2~: gl) W~S caï~ d ~n ~lr at 600~C for ~bout i.5 hour~. ~h~ calc~ne~ pr~auc~ was t:) ~rac~Eiz~d ~y ~he ac~y powd@r ~l~f~c'cion p~tterrl o~ ~bl~
~elow:
a~13~ ~4 ., .
,: :
., ~, , ~
~Z~ 7~
~ABLE A
2a d, (A)Relative Intensity 7,.4 llog5 vs 12.9 6.8~ w 19 . 7 4 . 51 m 210 2 4 .19 m ~2.4 30~7 s 25.9 3.440 m ~ he cal~ined T~PO-5 cvmpositions for which x-ray powd~r diffraction data ~ave been obtained ~o date have patterns which are characterized by the x ray powder diffrac ion pattern shown in Table B, below:
TAELE B
2~ d, ~A) 100 x I/I O
7.4 11.95 100 12~,9 6.~6 17 1~,,9 5.g5 7 19.7 4 ~ ~127 21.2 4. 19 39 210~* ~1,.08 8 22~4 3~97 7a 24 ~ 3~5~1 9 - 25 9 3.4'1025 2!3o~ 3~7~ 13 3t~0 2~197813 33~7 ~2~660 4 34~5 ~6~)0 9 3 ~ 4 3 1~ 4 37~8 2~31~ 10 42~3 ;2~137~2 ~3~1 2~)99 2 47~7 105il07q * peak may contain an impurl'cy D-13 ,854 7~
EXAMP~E 32 (a) TAPO-ll, as referred to in example 10, was subjected to xray analysisO
TAPO-ll was determined to have a ~haracteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table VII, below:
TABLE VII
2~ d,~A) Relative Intensi~y 9.5 9~31 m 20.5 4.33 m 2~.9 ~.~S vs 2~2 4.00 s .
~2~5 3.93 s 23.2 3.83 s All of the a~-synthesized TAPO-ll ~ompositions for which x-ray powder diffrac~ion data have been obtained t4 date have patterns which are characterized by ~he data of Table VI~I, below:
2~ d,(A) 100 x I/I O
~1 10~92 3~; -9 o 59 D 31 5~i 13 o ~ 71 17 1~7 5~;4 32 1603 5~44 5 19.0 d~67 7 20~5 4033 52 20~9 D.~25 100 22~2 4~0Q 67 22~6 3~93 73 ;23~2 3.1~3 74 2408 3~5~ I 5 2~o~ 3~376 17 26~6 3~3~;1 19 D~13,854 ~z TABLE VIII ~Continued) 2~ d, (A) 100x I/I 0 28.~ 3.143 --28 . 7 3 . 110 18 29.1 30069 8 29~5 2.52B 10 31,5 2.~40 12 33.0 2.714 19 34 .3 2,. 614 11 3~. 7 2 . 515 6 36~6 2.,456 7 37.~ 2.392 1~
37~8 2.381~ 16 39.3 2.29~ 4 ~2 .2 2. 141 4 42 . B 2.113 5 4500 2. ~14 6 46.0 1.973 3 47.1 1.92g 3 4~1 1.892 3 4B.9 1.863 5 50.8 1.797 6 5~.8 1.675 (b3 A portion of the assynthesized TAP0-11 of part a) was calcined in air at 550C for 1.5 hours. The calcined product was characterized by the x-ray powder dif fraction pa'ctern of Table C, below:
TABL}: C
2~ d~ (A) 100 x I/I O
__ 9.8 9.03 m :L601 5. 51 n~
~1.9 4006 vs 22.4 3.97 m 23,5 3,.79 m 29~7 3Oal08 m D-13 ,854 ~7~
~1 -All of the ~alcined TAPO-ll compositions for which x ray powder diffraction data have been obtained to date have patterns which are ~haracterized by the data of Table D, below:
TABLE V
29 d t (A) 100 x I/I O
8~ 1 10~ 92 22 9~8 9~03 J,2 L~7 7~S6 7 12~8 6~92 22 13 ~ 7 6 r 4 6 9 14.~i 6~07 6 16~ 1 5 ~ 51 54 ~, 170~ 5~07 6 19.5 (sh)4.55 19 1909 ~.~6 25 20.8 4.27 12 21.9 4.0~ 100 22.4 (sh)3.g7 54 23.~ 3.79 57 2400 3.71 20 2403 (sh)3.66 17 25~8 ~.453 24 26.7 3.339 16 27.2 3.278 ~8 27.~ 3.209 22 28.6 3.~21 10 29.7 3.~8 32 30.4 2.94~ 19 31.8 ~.~14 12 32.6 2.755 34~0 2.637 12 34 ~ 5 2 a 600 7 35~6 ;~5~!2 14 37.2 2.417 11 38.2 (sh~2.356 6 38.6 2.33~ lS
41~0 2~201 1 ~3.6 2.07 4~ 2.~3~ ~
45.2 2.006 4 49.1 1.85~ 11 ~9.6 1~38 . 10 50~4 lo Bll 4 52~ 746 d~
53~7 1.71~7 5 7 1~678 4 ~-13~B54 .
7~f~
~ ~2 -a) TAP0-18, as referred to in example 15, was subjected to x-ray analysis. TAP0-18 was de ermined to have a characteristic x-ray pswder diffraction pattern which contains at least ~he d-spacings set ~orth in Tabl~ IX below:
T~BLE IX
d,(A)Relative Intensity ,.
~ . 643 9 . 17 vs 16.87g 5025 m 170961 5.20 m 22.227 4.00 m 25 . 3 54 3 . 513 m 25.462 3,.498 m 26.~85 341 s b~ ~11 o the as-synthesized TAP0-18 compositions ~or which X-ray powder diffraction da'ca have been obtained to date have patterns which are characterized by the data of Table X, below:
TABLB X
d, (A)100 x I/I ,~
__ g ~643 9 o 1~ 10~) 10~474 8~15 3 :IL1.t~35 g~2 5 :~L3.1!~3 ~6~71 2 lq.~)55 6~30 3 14~E~34 5~97 3 15~55~ io70 12 ~L~o879 5~25 28 17~ 5~2~ 29 17~. 943 4 ~ 514 ~!0 18.!31~;7* 4~6~3 12 19~3 4~6 1~o556 4~3 2 20~ 210 4 ~ 3 9 2 20~729 4~29 3 D~13 D~54 ~L2~7~
~ 43 --TABLE X (Continued~
d, ~A)100 x I/I O
-21.0~10 4.22 22 22.227 4.~0 27 23.404 3.80 3 23.978 3.71 4 24.478 3.64 7 24.,6 ~h) 3~,62 --25000~ 3.5~2 11 25.3~1* 3.513 34 25.4~2 3.~8 32 ~6.173 3~401 6 26.685 3.340 60 2?.4 3.,26û
28.1D~9 3.17~ 15 2~.327 3.045 30,135 20966 13 30.877 2.896 5 31.428 2.8~6 9 31.~99 2.~05 32.525 20753 17 33.542 2.672 3 34 ~4 Sl 2 o603 2 34O547* 2~596 2 3 6 ~ 10 0 2 ~ 8 ~3 37~833 2~378 3 38,051 2.3~5 2 38.35~ 2.347 2 38.501 2.338 2 39.9 ~t.26 41 ~890 2 ~ 157 3 ~3~123 2~09~3 3 43~6 2.t)~10 ~5.3~12* 2~0t~0 6 46.795* 1~,941 B
~7.372~ ~.91~ ~
~708~7 ~.899 6 4 8 . 731* l o B 67 15 49.67~ 35 6 ~O.û5~ 22 2 5~ ,. 159 1.785 2 52.11~1 1.755 2 5~.0~1 1c696 2 54.2~9 1.691 2 54.671 1.,678 3 55.260 1.662 3 *peak may c~n~aI;~b~jCrity 8h c shoulder 3 ,~5~
, ~2~ 7 ~ ) ~APO-lB, as referred to in example 15, was subjected to X-ray analysis after calcination at 550C in air for 1 hour. T~PO-18 was determined to have a characteris'cic X-ray powder diffraction pattern which contains at least the d-spacing set forth in Table E, below:
TABLE E
2~ d, ~elatiYe Intensi~cy 9 . ~ 9 . 31 ~s 9-~ ~.21 YS
21.8 4.0~ m 22.9 3~88 w 29.0 3.079 m 31.0 2~,885 m b) ~11 of ~he ~alciried TAPO-18 compositions for whach X-ray powder diffraction data have been obtained to date have patterns which are charac'cerized by the data of Table F, below:
TAB
2~ d, (A) 150 x I/I O
___ 9~5 g.31 97 9~ 6 9 ~ 21 lt~t~
10.~; 8035 10 11~2 7 o 90 1~
13~4 ~161 113 14~4 6~ lS 10 16.0 5~5~1 13 L6~5 5~37 5 1~ ~ 1 5 ~ 1~ 18 1804 4~82 ~;
l9oO ~1.67 7 19,.5 ~a~s5 3 20~7 4~o29 13 D 13 ,854 ~73L~
TABLE F (Continued~
d,(A~ 100 x I/I O
21.8 4.08 46 22.9 3.88 15 24.2 3.68 11 24.7 3.60 10 25.5 3.493 8 26.2 3.401 7 27.1 3.290 1~
27.5 (sh~ 3.243 --28.2 3.164 5 29.0 3.~79 21 ~9.4 3.038 10 29~8 2.998 10 31.0 2.885 23 31.5 2.840 12 31.9 2.805 7 32.4 2.763 6 33.1 2.706 8 33.7 2.660 11 34.6 2.592 5 35.5 2.529 6 36.9 2.436 6 3~.9 2.315 5 42.7 2.118 44.7 2.027 3 46.8 1.941 2 47.8 1.903 4 49.3 1.848 2 49.7 1.834 3 51.8 1.765 4 54.0 1.698 3 a~ TAPO-20, as referred to in example 17, was subjected to X-ray analysis. T~PO-20 was determined to have a characteristic X-ray powder diffraction pattern which contains at least the d-spacings se~ forth in Table XI, below:
D-13,854-C
3 r~
~i TAELE XI
2a d, lA)Relative Intensity 14.0 6.33 m 19.8 4.48 m 24.~ 3.65 vs 23.2 3.164 m 31.6 2.831 w 34~6 2.~ w All of the as-~ynthe~ized TAP0-20 composit~ons for which X~ray powd~r difractiorl data have been ob~ained ~o da'ce have pa~terns which are characterized by the data of Table XII, below.
.
TABLE X I I
2~ d, (i~lOa x I/I O
14.0 6.33 52 19.8 4.4~ 46 21.3* ~a.17 2 21~9* ~.06 2203 3~g9 ~
22.5 (~h) 3.95 --23.0* 3.87 2 24~ 3.65 100 28.2 30164 21 31.5 20~31 12 3406 ~.592 17 37.,~ 2.3g2 --38.~* 27344 2 40.2 2420,3 ~2.9 2.108 5 ~7. ~ 1 . 903 2 52.2 1.752 12 . ~ .
~h - shoulder * peak may ~ontain an impuri'cy b~ A por~ on of the as-~ynthesiz~d T~ 20 o~ part a) was calcined in air at 550~C ~or D-13, 854 .~
~2~
1.0 hour. The calcined product was characterized by the X-ray powder diffraction pattern containing at least the d-spacing of Table G, below:
TABLE G
d,(A)Relative Intensity 14.3 6.19 vs 20.2 4~40 w 24.6 3.62 m 2~.5 3.132 w 31.8 2.~14 vm 35.0 2.564 w All the calcined TAPO-20 compositions for which X-ray powder diffraction data have been obtained to date have patterns which are characterized by the X-ray powder diffraction pattern of Table H, below:
TABLE H
d,(A)100 x I/I O
14.3 6.19 100 20.2 4.40 15 22.5 3.95 5 24.6 3.62 48 28.5 3.132 11 31.8 2.~14 9 35.0 2.564 10 37.9 2.374 40.7 2.217 2 43.2 ~.100 2 48.2 1.888 2 5~.6 1.740 6 a) TAPO-31, as referred to in example 18, was subjected to X-ray analysis. TAPO-31 was D-13,854-C
. . .
~7~7~
determined to have a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIII, below:
TABLE XIII
20 d,(A)Relative Intensity 8.510.40 m 20.9 4.25 s 21.~ 4.19 s 22.5 3.95 vs 22.7 3.92 vs All of the as-synthesi2ed TAPO-31 compositions for which X-ray powder diffraction data have been obtained to date have patterns which are characterized by the data of Table XIV, below:
TABLE XIV
20 d,(A~100 x I/I O
7.012.63 21 8.510.40 56 9.6 g.21 2~
9.8 (sh) 9.03 --11.8*7.50 10 13.3 6.56 9 13.8 6.42 13 14.8 5.99 4 15.8 5.~1 7 17.0 5.22 4 18.4 4.8~ 8 19.1 4.65 5 20.2 (sh) 4.40 --20.4 4.35 48 20.~*4.25 60 21.2 4.19 68 22.0 4.04 43 22.5*3.95 9~
22.7 3.92 100 23.3 (sh) 3.82 35 24.6 (sh) 3.62 _._ D-13,854-C
., ~
~ ~ ~' t ,. . .
~h~7~
~ g TABLE X~V ~ContinuedL
2B d, IA)lOC x I/I 0 25.4 305~7 16 2603 ( h) * 3.389 --26.5* 30363 50 26.7 (sh) ~ 3.339 --27.8 3.209 ~3 2~. 2 3 . 1~4 --28.B* 3.100 8 2~.6 3~ 6 30.0 ~.97g 5 31.5~ 2~B40 14 33.0 - 2.714 5 33.6 2.6Ç7 S
35.1 2.557 7 35.9 2.501 8 37.B 2.380 13 40.0 20254 7 ~2.2 2.141 16 49.7 1.834 12 -~h - ~houlder * peak may contain an impurity b) ~ portion of the as-synthesized TAP0-31 of part a) was calcined in air at 550C for 1.0 hour~. The calcin~d product was characterized by the X-ray powder diffraction pattern of Table M, below:
. TA3LE 11 d, ~A3Rela~ive Intensity 8.5~ 4~ YS
9.8 9.03 w 20~3 4.37 m . 0 2 .6 . 3.93 vs 31~7 2.823 m D-13 ,854 . ~
7~
All the calcined TAPO-31 compositions ror which X-ray powder diffraction da~a have been ohtained to date have patterns which are haracterized by the data of Table N, below:
TABLE ~
d,(A)100 x I/I O
5.8* 15.24 3
6.6* 13.39 4 8.5 10.40 100 9.8 9.03 17 12.8* 6.92 6 13.5 6.56 9 14.8 5.9~ 8 16.2 5.47 9 17.0 5.22 11 1~.4 4.82 6 20.3 4.37 50 21.7 (sh) 4.10 22.1 4.02 60 22.6 3.93 96 23.0 tsh) 3.87 __ 23.~ 3.79 16 25.2 3.534 14 25.7 3.466 16 28.0 3.187 16 29.7 3.00~ 17 30.3 2.9~0 6 30.9 2.894 5 31.7 2.823 27 32.5* 2.765 6 35.1 2.556 12 36.2 2.481 5 37.2 2.417 6 38.2 2.356 6 39,4 2.2B7 40.2 2.243 6 44.~ 2.~5~ ~
45.0 2.014 4 46.6 1.950 5 47.6 1.910 4 4~.6 1.873 5 49.1 1.~55 4 50.9 1.79~ 4 51.6 1.771 6 sh = shoulder * peak may contain an impurity D-13,854-C
a) TAPO-33, as referred to in example 20, was subjected to X-ray analysis. TAPO-33 was determined to have a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XV, below:
TABLE XV
d,~A) P~elative Intensity 9.3 9,51 m 12.6 7.03 vs 20.5 4.33 m 23.9 3.72 m 26.1 3.414 m 27. 4 3.255 s All of the as-synthesiæed TAPO-33 compositions for which X-ray powder diffraction data have been obtained to date hav~ patterns which are characterized by the data of Table XVI, below:
TABLE XVI
d,(A) 100 x I/I O
9.3 9.51 2~
12.6 7.03 lO0 13.9* 6.37 3 15.3 5.79 14 17.0 5.22 13 17.5 5.07 1 18.0 4.93 19.~ 4.58 3 19.8 (sh)* 4.43 --20.5 4.33 22 20.9 4.25 3 22.2 ~.00 3 23.0 3087 5 ~3.9 3.72 26 24.3 3.66 5 D-13,854-C
~2~7~
TABLE XVI ~Continue~
2~ d, (A) 100 x 25.0 3.552 ~
26.1 3.414 28 2704 3,,255 77 28 . 2 (sh) 3 ,164 ~~
~9.5 3.028 13 3~.7 20912 6 31.4 2.84B
32.0 2.7~7 8 32.6 2.. 7~7 34.3 2.614 8 35,.~ 2.543 2 36.8 244~2 2 37.8 2.3~0 3 39.0 2.309 2 39.~ 2.,286 40.3 2~238 2 41.5 2.176 2 45.2 200~ii 2 46.8 1.941 4 47~, 8 1. 903 7 4g.4 1.8~5 2 49.8 1.~31 52,.0 1.758 6 ~2.8 1.734 6 54.0 1.698 2 54.4 1.~1 3 ~.2 1.~4 l~
.
sh = ~houlder * peak may con'cain an impurity b~ A portion of the a~=synthesized TAP0-33 of par'c a) was calcined in air at 550C for 1 hour. The calcined product was characterized by the X-r~y powder difraction pat~ern of Table 0, below o D-13,854 ,.
" ~ -:~Z~7~
~3 TABL~ o 2a ~ Rel~t~ve In~en8lty 9.5 ~.31 13 . 2 ~ 0 71 Y5 18.1 40gO m ~1 . 2 ~ . 19
45.0 2.014 4 46.6 1.950 5 47.6 1.910 4 4~.6 1.873 5 49.1 1.~55 4 50.9 1.79~ 4 51.6 1.771 6 sh = shoulder * peak may contain an impurity D-13,854-C
a) TAPO-33, as referred to in example 20, was subjected to X-ray analysis. TAPO-33 was determined to have a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XV, below:
TABLE XV
d,~A) P~elative Intensity 9.3 9,51 m 12.6 7.03 vs 20.5 4.33 m 23.9 3.72 m 26.1 3.414 m 27. 4 3.255 s All of the as-synthesiæed TAPO-33 compositions for which X-ray powder diffraction data have been obtained to date hav~ patterns which are characterized by the data of Table XVI, below:
TABLE XVI
d,(A) 100 x I/I O
9.3 9.51 2~
12.6 7.03 lO0 13.9* 6.37 3 15.3 5.79 14 17.0 5.22 13 17.5 5.07 1 18.0 4.93 19.~ 4.58 3 19.8 (sh)* 4.43 --20.5 4.33 22 20.9 4.25 3 22.2 ~.00 3 23.0 3087 5 ~3.9 3.72 26 24.3 3.66 5 D-13,854-C
~2~7~
TABLE XVI ~Continue~
2~ d, (A) 100 x 25.0 3.552 ~
26.1 3.414 28 2704 3,,255 77 28 . 2 (sh) 3 ,164 ~~
~9.5 3.028 13 3~.7 20912 6 31.4 2.84B
32.0 2.7~7 8 32.6 2.. 7~7 34.3 2.614 8 35,.~ 2.543 2 36.8 244~2 2 37.8 2.3~0 3 39.0 2.309 2 39.~ 2.,286 40.3 2~238 2 41.5 2.176 2 45.2 200~ii 2 46.8 1.941 4 47~, 8 1. 903 7 4g.4 1.8~5 2 49.8 1.~31 52,.0 1.758 6 ~2.8 1.734 6 54.0 1.698 2 54.4 1.~1 3 ~.2 1.~4 l~
.
sh = ~houlder * peak may con'cain an impurity b~ A portion of the a~=synthesized TAP0-33 of par'c a) was calcined in air at 550C for 1 hour. The calcined product was characterized by the X-r~y powder difraction pat~ern of Table 0, below o D-13,854 ,.
" ~ -:~Z~7~
~3 TABL~ o 2a ~ Rel~t~ve In~en8lty 9.5 ~.31 13 . 2 ~ 0 71 Y5 18.1 40gO m ~1 . 2 ~ . 19
7 3.33!~
~2.0 20797 nn ~ 11 of the cal~ined TAP0-33 composi~ions fo~ whi~a X-r~y powd2r ~iffr~c~on d~a have been okt~ined to ~a~e h~ve p~'cterns which are chara~te~ized ~y th~ data of Table P 9 below:
~ABLi: ~
2~ d, IA)100 a: I~I 0 9.5 9,.31 ~7 13.2 6.7~ 1~0 14,.1 ~.2~ ~1 34.6 ~.07 11 ï5 . ~ ~ . 91 23 15.B 5061 16 ~801 ~9û ~9 1~.4 4~2 31 lB.9~ 407Q 27 2001 ~.~2 2~1 ~192 q,.l9 63 22.5 3.9~ 18 24.2 3.C~ 1 2qo~ 3~ 2 ?5 0 3 (~h~ 3 ~, 520 ~5~4 ~05~ ~6 3.~4~ 13 .7 3.33~ 41 ~7.0 3~ 2 24 28 . ~ ~h) 3 a 14 3 ~D
28.9 34~9 ~
29~,~ 30~48 ~L7 3~.2 2.95~ 29 30.g~ ~.8~4 ~4 3~.5 ~0 2~840 a2 32.~ 2.79'1 ~4 D~13 ~5~
~, `:
... . . .. . . . . .. .....
~Z~7~
3A~5~
2~ d~ (A) 100 x I/I
33 .0 2. 714 10 33,g 2.64~ 10 34.4 2.607 7 36.9 2~36 7 37.3 2.~111 8 38.2 2.35S 1 3~.6 ~.332 8 39.1 2.303 7 391~9 ~.2~ 5 40 . 8 ~ . 21ï . 6 42.3 2.137 4 O 3 ~ S
~17.8 1.90~ 9 ~h ~ shoulder * peak may corltain an ~mpurity In order to demonstrate the catalytic:
activity of the TAPO compositions, calcined ~amples o~E the products of- ~xamples 1, 11, 12, 14, 18 and 20 were then tested ~or ca~calytic crackinge Further, c:omparative examples were s:arried ou'c to provide compositions with AlPO4-5 gexample 44;, amorphous TiO~ and 95 wt ~ AlPO4~18 (example 46). The AlPO4-~ and ~lPO4~18 were prepared as described in exampl~s 1-~6 and 46 of U.SO Paten~: ~o., 4,310~440~ The ~morphc~us TlO;~ (example 45~ was prepared using 1709 grams of ti~anium isopropoxide which was hydrolyzed using 45O5 grams of water ~nd 23.0 grams of phosphoric acid and then fil~ering and washing ~he producS. ~he ~e~t procedure em~loy~d wa~ the ~atalyti~: ~racking o$ premixed two t~) mole % n-butan~ i~ h~lium ~ream ~n a 1/2~ O.D., gu. ~t~
tube reactor over up to about 5 grams (20~410 mesh) of the part icular TAPO ~ample ~co be tested O The ~-13,~54 fl~
sample was activated n situ for 60 minutes at 500C
under 200 cm3/min dry helium purge. Then the two (2) mole ~percent) n-butane in helium at a flow rate of 50 cm3/min was passed over the sample for 40 minutes with product stream analysis being carried out at 10 minu-te intervals. The pseudo-first-order rate constant (ka) was then calculated to determine the catalytic activity of the TAPO
composition. The ka value (cm3/g min) obtained for the TAPO compositions are set forth, below, in Table XVII.
ABLE XVII
Example SamPle Rate Constant (ka) 38 Ex. 1 0.17 39 Ex. 11 0.12 Ex. 12 0.07 41 Ex. 14 0.25 42 Ex. 18 0.1 43 Ex. 20 0.2 44 Comparative 0.05 Comparative 0.4 46 Comparative 0.08 D-13,854-C
~2.0 20797 nn ~ 11 of the cal~ined TAP0-33 composi~ions fo~ whi~a X-r~y powd2r ~iffr~c~on d~a have been okt~ined to ~a~e h~ve p~'cterns which are chara~te~ized ~y th~ data of Table P 9 below:
~ABLi: ~
2~ d, IA)100 a: I~I 0 9.5 9,.31 ~7 13.2 6.7~ 1~0 14,.1 ~.2~ ~1 34.6 ~.07 11 ï5 . ~ ~ . 91 23 15.B 5061 16 ~801 ~9û ~9 1~.4 4~2 31 lB.9~ 407Q 27 2001 ~.~2 2~1 ~192 q,.l9 63 22.5 3.9~ 18 24.2 3.C~ 1 2qo~ 3~ 2 ?5 0 3 (~h~ 3 ~, 520 ~5~4 ~05~ ~6 3.~4~ 13 .7 3.33~ 41 ~7.0 3~ 2 24 28 . ~ ~h) 3 a 14 3 ~D
28.9 34~9 ~
29~,~ 30~48 ~L7 3~.2 2.95~ 29 30.g~ ~.8~4 ~4 3~.5 ~0 2~840 a2 32.~ 2.79'1 ~4 D~13 ~5~
~, `:
... . . .. . . . . .. .....
~Z~7~
3A~5~
2~ d~ (A) 100 x I/I
33 .0 2. 714 10 33,g 2.64~ 10 34.4 2.607 7 36.9 2~36 7 37.3 2.~111 8 38.2 2.35S 1 3~.6 ~.332 8 39.1 2.303 7 391~9 ~.2~ 5 40 . 8 ~ . 21ï . 6 42.3 2.137 4 O 3 ~ S
~17.8 1.90~ 9 ~h ~ shoulder * peak may corltain an ~mpurity In order to demonstrate the catalytic:
activity of the TAPO compositions, calcined ~amples o~E the products of- ~xamples 1, 11, 12, 14, 18 and 20 were then tested ~or ca~calytic crackinge Further, c:omparative examples were s:arried ou'c to provide compositions with AlPO4-5 gexample 44;, amorphous TiO~ and 95 wt ~ AlPO4~18 (example 46). The AlPO4-~ and ~lPO4~18 were prepared as described in exampl~s 1-~6 and 46 of U.SO Paten~: ~o., 4,310~440~ The ~morphc~us TlO;~ (example 45~ was prepared using 1709 grams of ti~anium isopropoxide which was hydrolyzed using 45O5 grams of water ~nd 23.0 grams of phosphoric acid and then fil~ering and washing ~he producS. ~he ~e~t procedure em~loy~d wa~ the ~atalyti~: ~racking o$ premixed two t~) mole % n-butan~ i~ h~lium ~ream ~n a 1/2~ O.D., gu. ~t~
tube reactor over up to about 5 grams (20~410 mesh) of the part icular TAPO ~ample ~co be tested O The ~-13,~54 fl~
sample was activated n situ for 60 minutes at 500C
under 200 cm3/min dry helium purge. Then the two (2) mole ~percent) n-butane in helium at a flow rate of 50 cm3/min was passed over the sample for 40 minutes with product stream analysis being carried out at 10 minu-te intervals. The pseudo-first-order rate constant (ka) was then calculated to determine the catalytic activity of the TAPO
composition. The ka value (cm3/g min) obtained for the TAPO compositions are set forth, below, in Table XVII.
ABLE XVII
Example SamPle Rate Constant (ka) 38 Ex. 1 0.17 39 Ex. 11 0.12 Ex. 12 0.07 41 Ex. 14 0.25 42 Ex. 18 0.1 43 Ex. 20 0.2 44 Comparative 0.05 Comparative 0.4 46 Comparative 0.08 D-13,854-C
Claims (45)
1. Crystalline molecular sieves comprising pores having nominal diameters of greater than about 3 Angstroms and whose chemical composition in the as-synthesized and anhydrous form is represented by the unit empirical formula:
mR:(TixAlyPz)O2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (TixAlyPz)O2 has a value of between zero and about 5.0; the maximum value in each case depending upon the molecular dimensions of the templating agent and the available void volume of the pore system of the particular titanium molecular sieve; "x", "y" and "z" represent the mole fractions of titanium. aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D and E of the ternary diagram which is Fig. 1 of the drawings, said points A, B, C, D and E
representing the following values for "z", "y" and "z":
mR:(TixAlyPz)O2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (TixAlyPz)O2 has a value of between zero and about 5.0; the maximum value in each case depending upon the molecular dimensions of the templating agent and the available void volume of the pore system of the particular titanium molecular sieve; "x", "y" and "z" represent the mole fractions of titanium. aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D and E of the ternary diagram which is Fig. 1 of the drawings, said points A, B, C, D and E
representing the following values for "z", "y" and "z":
2. The crystalline molecular sieves according to claim 1 wherein the mole fractions of titanium, aluminum and phosphorus are within the pentagonal compositional area defined by points a, b, c, d and e of the ternary diagram which is Fig. 2 of the drawings, said points a, b, c, d and e of the ternary diagram which is Fig. 2 of the drawings, said points a, b, c, d and e representing the following values for "x", "y" and "z".
3. The crystalline molecular sieve of claims 1 or 2 having the characteristic X-ray powder diffraction pattern set forth in Table V.
4. The crystalline molecular sieve of claims 1 or 2 having the characteristic X-ray powder diffraction pattern set forth in Table VII.
5. The crystalline molecular sieve of claims 1 or 2 having the characteristic X-ray powder diffraction pattern set forth in Table IX.
6. The crystalline molecular sieve of claims 1 or 2 having the characteristic X-ray powder diffraction pattern set forth in Table XI.
7. The crystalline molecular sieve of claims 1 or 2 having the characteristic X-ray powder diffraction pattern set forth in Table XIII.
8. The crystalline molecular sieve of claims 1 or 2 having the characteristic X-ray powder diffraction pattern of Table XV.
9. Crystalline molecular sieves comprising a composition expressed in terms of the mole ratios of oxides in the anhydrous form as:
vR : p TiO2 : q Al2O3 : r P2O5 wherein "R" represents at least one organic templating agent; "v" represents an effective amount of organic templating agent; "p", "q" and "r"
represent moles, respectively, of titanium, alumina and phosphorus pentaoxide based on said moles being such that they are within the pentagonal compositional area defined by point A, B, C, D and E of the ternary diagram which is Fig. 1 of the drawings, said points A, B, C, D and E representing the following values for "p", "q" and "r".
vR : p TiO2 : q Al2O3 : r P2O5 wherein "R" represents at least one organic templating agent; "v" represents an effective amount of organic templating agent; "p", "q" and "r"
represent moles, respectively, of titanium, alumina and phosphorus pentaoxide based on said moles being such that they are within the pentagonal compositional area defined by point A, B, C, D and E of the ternary diagram which is Fig. 1 of the drawings, said points A, B, C, D and E representing the following values for "p", "q" and "r".
10. The crystalline molecular sieves of claim 9 wherein "p", "g" and "r" are preferably within the pentagonal compositional area defined by point a, b, c, d and e of the ternary diagram which is Fig. 2 of the drawings, said points a, b, c, d and e representing the following values for "p", "q"
and "r":
and "r":
11. The crystalline molecular sieves of claim 1 wherein the molecular sieves have been calcined.
12. The crystalline molecular sieves of claim 2 wherein the molecular sieves have been calcined.
13. The crystalline molecular sieves of claims 11 or 12 having the characteristic X-ray powder diffraction pattern set forth in any one of Tables A, C, E, G, M or O.
14. The crystalline molecular sieves of claims 11 or 12 wherein such are calcined in air at a temperature between about 200°C and about 700°C
for a period of time sufficient to remove at least a portion of template R.
for a period of time sufficient to remove at least a portion of template R.
15. Process for preparing a titanium-containing molecular sieve as set forth in Claim 1 which comprises forming a reaction mixture containing reactive sources of TiO2, Al2O3, and P2O5 and an organic templating agent, said reaction mixture comprising a composition expressed in terms of molar oxide ratios of:
f R2O : (TixAlyPz)O2 : gH2O
wherein "R" is an organic templating agent, "f" has a value large enough to constitute an effective amount of "R"; "g' has a value of from zero to 500;
"x", "y" and "z" represent the mole fractions, respectively, of titanium, aluminum and phosphorus in the (TixAlyPz)O2 constituent, and each has a value of at least 0.001 and being within the quatrilateral compositional area defined by points, h, i, j and k which is Fig. 3 of the drawings, said points h, i, j and k representing the following values for "x", "y" and "z":
f R2O : (TixAlyPz)O2 : gH2O
wherein "R" is an organic templating agent, "f" has a value large enough to constitute an effective amount of "R"; "g' has a value of from zero to 500;
"x", "y" and "z" represent the mole fractions, respectively, of titanium, aluminum and phosphorus in the (TixAlyPz)O2 constituent, and each has a value of at least 0.001 and being within the quatrilateral compositional area defined by points, h, i, j and k which is Fig. 3 of the drawings, said points h, i, j and k representing the following values for "x", "y" and "z":
16. Process according to Claim 15 wherein "g" has a value of from 2 to 50.
17. Process for preparing a crystalline silicoaluminophosphate of Claim 1 which comprises forming a reaction mixture having a composition expressed in terms of molar oxide ratios of:
oR2O : wM2O : (TixAlyPz)O2 : nH2O
wherein "R" is an organic templating agent; "o" has a value great enough to constitute an effective concentration of "R" and is within the range 0 to 1;
"M" is an alkali metal cation; "w" has a value of zero to 2.5; "n" has a value of from zero to 500;
"x", "y" and "z" represent the mole fractions, respectively, of titanium, aluminum and phosphorus in the (TixAlyPz)O2 constituent, and each has a value of at least 0.001 and being within the quatrilateral compositional area defined by points, h, i, j and k which is Fig, 3 of the drawings, said points h, i, j and k representing the following values for "x", "y" and "z":
oR2O : wM2O : (TixAlyPz)O2 : nH2O
wherein "R" is an organic templating agent; "o" has a value great enough to constitute an effective concentration of "R" and is within the range 0 to 1;
"M" is an alkali metal cation; "w" has a value of zero to 2.5; "n" has a value of from zero to 500;
"x", "y" and "z" represent the mole fractions, respectively, of titanium, aluminum and phosphorus in the (TixAlyPz)O2 constituent, and each has a value of at least 0.001 and being within the quatrilateral compositional area defined by points, h, i, j and k which is Fig, 3 of the drawings, said points h, i, j and k representing the following values for "x", "y" and "z":
18. Process according to Claim 15 or Claim 17 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid.
19. Process according to Claims 15 or 17 wherein the source of aluminum in the reaction mixture is at least one compound selected from the group consisting of pseudo-boehmite and aluminum alkoxide, and the source of phosphorus is orthophosphoric acid.
20. Process according to Claims 15 or 17 wherein the aluminum source is aluminum isopropoxide.
21. Process according to Claims 15 or 17 where the organic templating agent is selected from the group consisting of quaternary ammonium or quaternary phosphonium compounds of the formula R4X+
wherein X is nitrogen or phosphorous and each R is alkyl containing between 1 and about 8 carbon atoms or aryl.
wherein X is nitrogen or phosphorous and each R is alkyl containing between 1 and about 8 carbon atoms or aryl.
22. Process according to Claims 15 or 17 wherein the templating agent is selected from the group consisting of tetrapropylammonium ion;
tetraethylammonium ion; tripropylamine;
triethylamine; triethanolamine; piperidine;
cyclohexylamine; 2-methyl pyridine;
N,N-dimethylbenzylamine; N,N-diethylethanolamine;
dicyclohexylamine; N,N-dimethylethanolamine;
choline; N,N-dimethylpiperazine;
1,4-diazabicyclo-(2,2,2) octane; N-methylpiperidine;
3-methylpiperidine; N-methylcyclohexylamine;
3-methylpyridine; 4-methylpyridine; quinuclidine;
, N,N-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;
tetramethylammonium ion; tetrabutylammonium ion, tetrapentylammonium ion; di-n-butylamine;
neopentylamine; di-n-pentylamine; isopropylamine;
t-butylamine; ethylenediamine and 2-imidazolidone;
di-n-propylamine; and a polymeric quaternary ammonium salt [(C14H32N2)]x wherein x is a value of at least 2.
tetraethylammonium ion; tripropylamine;
triethylamine; triethanolamine; piperidine;
cyclohexylamine; 2-methyl pyridine;
N,N-dimethylbenzylamine; N,N-diethylethanolamine;
dicyclohexylamine; N,N-dimethylethanolamine;
choline; N,N-dimethylpiperazine;
1,4-diazabicyclo-(2,2,2) octane; N-methylpiperidine;
3-methylpiperidine; N-methylcyclohexylamine;
3-methylpyridine; 4-methylpyridine; quinuclidine;
, N,N-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;
tetramethylammonium ion; tetrabutylammonium ion, tetrapentylammonium ion; di-n-butylamine;
neopentylamine; di-n-pentylamine; isopropylamine;
t-butylamine; ethylenediamine and 2-imidazolidone;
di-n-propylamine; and a polymeric quaternary ammonium salt [(C14H32N2)]x wherein x is a value of at least 2.
23. Process for separating mixtures of molecular species wherein such mixtures contain molecular species having different degrees of polarity and/or kinetic diameters comprising contacting said mixture with a composition of claims 1, 11 or 12.
24. Process for converting a hydrocarbon which comprises contacting said hydrocarbon under hydrocarbon converting conditions with a crystalline molecular sieve as set forth in claim 1.
25. Process according to claim 24 wherein the hydrocarbon conversion process is cracking.
26. Process according to claim 24 wherein the hydrocarbon conversion process is hydrocracking.
27. Process according to claim 24 wherein the hydrocarbon conversion process is hydrogenation.
28. Process according to claim 24 wherein the hydrocarbon conversion process is polymerization.
29. Process according to claim 24 wherein the hydrocarbon conversion process is alkylation.
30. Process according to claim 24 wherein the hydrocarbon conversion process is reforming.
31. Process according to claim 24 wherein the hydrocarbon conversion process is hydrotreating.
32. Process according to claim 24 wherein the hydrocarbon conversion process is isomerization.
33. Process according to claim 24 wherein the isomerization is xylene isomerization.
34. Process according to claim 24 wherein the hydrocarbon conversion process is dehydrocyclization.
35. Process for converting a hydrocarbon which comprises contacting said hydrocarbon under hydrocarbon converting conditions with a crystalline molecular sieve as set forth in claim 11.
36. Process according to claim 35 wherein the hydrocarbon conversion process is cracking.
37. Process according to claim 35 wherein the hydrocarbon conversion process is hydrocracking.
38. Process according to claim 35 wherein the hydrocarbon conversion process is hydrogenation.
39. Process according to claim 35 wherein the hydrocarbon conversion process is polymerization.
40. Process according to claim 35 wherein the hydrocarbon conversion process is alkylation.
41. Process according to claim 35 wherein the hydrocarbon conversion process is reforming.
42. Process according to claim 35 wherein the hydrocarbon conversion process is hydrotreating.
43. Process according to claim 35 wherein the hydrocarbon conversion process is isomerization.
44. Process according to claim 43 wherein the isomerization is xylene isomerization.
45. Process according to claim 35 wherein the hydrocarbon conversion process is dehydrocyclization.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US480,738 | 1983-03-31 | ||
US06/480,738 US4500651A (en) | 1983-03-31 | 1983-03-31 | Titanium-containing molecular sieves |
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Publication Number | Publication Date |
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CA1217178A true CA1217178A (en) | 1987-01-27 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA000450658A Expired CA1217178A (en) | 1983-03-31 | 1984-03-28 | Titanium-containing molecular sieves |
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US (1) | US4500651A (en) |
EP (1) | EP0121232A3 (en) |
JP (1) | JPS59232903A (en) |
CA (1) | CA1217178A (en) |
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GB207171A (en) * | 1922-11-17 | 1924-06-19 | Nash Engineering Co | Improvements in or relating to condensation pumps |
US3448164A (en) * | 1967-09-21 | 1969-06-03 | Phillips Petroleum Co | Olefin skeletal isomerization and catalyst |
US4382854A (en) * | 1978-02-03 | 1983-05-10 | Kaiser Aluminum & Chemical Corporation | Ni/Co Mo P on titania-alumina hydrodesulfurizing catalyst and process of hydrodesulfurizing using the same |
DE3014950A1 (en) * | 1980-04-18 | 1981-10-29 | Basf Ag, 6700 Ludwigshafen | CATALYSTS FOR THE OLIGOMERIZATION OF OLEFINS |
US4310440A (en) * | 1980-07-07 | 1982-01-12 | Union Carbide Corporation | Crystalline metallophosphate compositions |
US4358397A (en) * | 1980-10-29 | 1982-11-09 | Mobil Oil Corporation | Zeolite catalysts modified with group IV A metals |
-
1983
- 1983-03-31 US US06/480,738 patent/US4500651A/en not_active Expired - Lifetime
-
1984
- 1984-03-28 CA CA000450658A patent/CA1217178A/en not_active Expired
- 1984-03-28 EP EP84103424A patent/EP0121232A3/en not_active Withdrawn
- 1984-03-30 JP JP59061296A patent/JPS59232903A/en active Pending
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EP0121232A3 (en) | 1987-03-25 |
US4500651A (en) | 1985-02-19 |
JPS59232903A (en) | 1984-12-27 |
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