Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
F-4690~47b5)
~L32~7~8
This invcn~ion relates to a syn~l)etic ~ystalline molecular
sievc ¢ompos;tion and in particular to a composition oorltainlng a
fra~cwolk +3 Yalence elemcnt, e.g. aluminum, a fra~work +5 valence
element, e.g. phos~horous, and prefera~ily a frcimc~ork ~4 val~nce
element, e.g. si~;c.on.
Zeolit;~. mc~terials, both na~.ural and syTthetic, have been
dcmonstrated ln t~ic past ~o have c~talytic propertie~ for vario
types of hydrocarbon co~version. Certain zeoli~ic materials are
ordered, porous crystalline aluminosi~icates havlng a deinite
~rystfllline struc~l~re as det~rmined by X-ray diffrac.~.;on, within
which thcre are cavities which may be interconnected by channels or
pores. Th~s~ cavities and pores are ~niform in size within a
spec.lfic zeoliti~ materia~. Sinc~ the dim¢n~ions of these pores are
~uc.~ a.~ ~ accept for adsorption molccule,s Or cert~ln di~ensions
while rejectin~ ~ho~e o larger dimension.s, thesc materials haivc
come to be known as "molecular sie~es" and ~re ut.~lized in a variety
of ways to take advant~igc of thesc properties.
Suc.h niolecular sieves, both natural and synthetic., ~nclude
a ~ide variety of po~itive ion-containing crystall~ne
~luminosili~ates. ~cse alu~inosilicatc~ ~an ~ie described as rigid
three-dimcnsionail ~rameworks of S;04 and ~04 ln whi~h th~
tetrahedra are cross-linked by the shclring of oxygen atoms whcreby
the r~tio of the total al-lniin~im ~r~id silicon atoms to oxygen atonls is
1:2~ The electrov~lcnce of the tetrahedrci contc~Jiining alum;num i$
balanced by the inclusion in tle ~.ryst~l o~ a ~ation, ~or example an
~lkali metal or aT~ alin~ earth mctal c~tion~ This can be
exprcssed whercin the ratio of alulninum ~o the numl~er o~ rarious
cations, such as Ca/Z, Sr/2? ~ ~ or Li, Is equal to ~ y. ~e
type of ~2tion may be e~lcl)al ged either entirely or partially with
~nother l;ype of c.ation utilizil~ ion e~change techniqu~s in a
.
:' ~
' . , . ~ ~, , . , :,
.~' ' . .
~ ~2~7~
F-4690(4765) --2--
conventional manner. By means of such cation exchange, it has been
possible to vary the properties of a given aluminosilicate by
suitable selection of the cation.
Prior art techniques have resulted in the formation of a
great variety of synthetic zeolites. The zeolites have come to be
designated by letter or other convenient symbols, as illustrated by
zeolite A (U.S. Patent 2,882,243), zeolite X (U.S. Patent
2,882,244), zeolite Y (U.S. Patent 3,130,Q07), zeolite ZK-5 (U.S.
Patent 3,247,195), zeolite ZK-4 (UOS. Patent 3,314,752), zeolite
ZSM-5 (U.S. Patent 3,702,8~6), zeolite ZSM-ll (U.S. Patent
3,709,979), zeolite ZSM-12 (U.S. Patent 3,832,449), zeolite 2SM-20
(U.S. Patent 3,972,983), zeolite ZSM-35 (U.S. Patent 4,016,245),
; zeolite ZSM-38 (U.S. Patent 4,0~6,859), and zeolite ZSM-23 (U.S.
Patent 4,076,842).
Aluminum phosphates are taught in, for example U.S.
Patents 4,310,440 and 4,385,994.
Silicoaluminophosphates o various structure are taught in
U.S. Patent 4,440,871. U.S. ~tent 4,363,748 describes a
combination of silica and aluminum-calcium-cerium phosphate as a low
l, 20 acid activity catalyst for oxidati~e dehydrogenation. Great Britain
-~ Patent 2,068,253 discloses a combination of siliça and
aluminum-calcium-tungsten phosphate as a low acid activity catalyst
for oxidative dehydrogenation. U.S. Patent 4,228,036 teaches an
alumina-aluminum phosphate-silica matrix as an amorphous body to be
mixed with zeolite for use as cracking catalyst. U.S. Patent
3,213,035 teaches improving hardness of aluminosilicate catalysts by
treatment with phosphoric acid. The catalysts are amorphous.
-~ The present invention resides in a novel synthetic
crystalline molecular sieve composition comprising at least 70% by
weight of a crystalline material having the X-ray diffraction lines
listed in ~able IA below:
:~
:.
- : , . .
, , , , ~. . -
, . . .
, ........................................ .
~29798
F-4690(4765) --3--
Table lA
Interplanar d-Spacings (A) Relative Intensity
16.4 1 O.Z YS
8.2 -+ 0.1 w
6.19 + 0.07 w
5.48 + 0.05 w
4-7~ + 0-05 w
and more specifically the following X-ray diffraction lines:
Table lB
Interplanar d-Spacings (A) Relative Intensity
16.4 + 0.2 vs
8.2 + 0.1 w
6.19 + 0.07 w
; 5.48 + 0.05 w
4.74 ~ 0.05 w
4.10 + 0.04 w
4.05 + 0.04 w
3 96 + 0 04 w
3.76 ~ 0.03 w
3.28 + 0.03 w
These X-ray diffraction data were collected with
' conventional X-ray systems, using copper K-alpha radiation. Thepositions of the peaks, expressed in degrees 2 theta, where theta is
the Bragg angle, were determined by scanning 2 theta. The
interplanar spacings, d, measured in Angstrom units (A), and the
relative intensities of the lines~ I/Io, where Io is
one-hundredth of the intensity of the strongest line, including
subtraction of the background, were derived. The relative
intensities are given in terms of the symbols vs = very strong
~ 30 (75-100%), s = strong (50-74%), m = medium (25-49%) and w = weak
- (0-24~). It should be understood that this X-ray diffraction
pattern is characteristic of all the species of the present
. . : . ., ~ . . , ~- . ..
; -, ., :
:, , : ~ . , .:
"' ' ' ~ " ' ' '
~32~7~
F-4690(4765~ --4--
compositions. Ion exchange of cations with other ions results in a
composition which reveals substantially the same X-ray diffracti~
pattern with some minor shifts in interplanar spacing and variatiDn
in relative intensity. ~elative intensity of individual lines ma~
also vary relative the strongest line when the composition is
chemically treated, such as by dilute acid treatment. Other
variations can occur, depending on the composition of the partic~ar
sample, as well as its degree of thermal treatment. The relative
intensities of the lines are also susceptible to changes by facta~s
such as sorption of water, hydrocarbons or other components in t~
channel structure. Further, the optics of the X-ray diffraction
equipment can have significant effects on intensity, particularly in
the low angle region. Intensities may also be affected by prefe~ed
crystallite orientation. In addition, the line at a d-spacing of
6.19 _ 0.07A is believed to be a doublet at 6.21 + 0.05A and 6.17 ~_
0.05A but in many cases the doublet is difficult to resolve.
The X-ray diffraction lines in Tables lA and lB identify a
cryst~l framework topology exhibiting large pore windows of
18-membered ring size. The pores are at least 12 Angstroms, e.g.
12-13 Angstrom, in diameter.
The crystalline framework of the composition of this
invention has the general chemical formula:
;
~XO ) :(YO )
2 l-y 2 l-x 2 x+y
wherein X is a +3 valence element, Y is a l5 valence element, Z i~
an optional ~4 valence element, and x and y are each greater than -l
and less than fl, with anions and/or cations being present as
necessary for electrical neutrality. Preferably, the element Z i5.
p~esent and x and y satisfy the further relationships:
(1) if x is 0, then y is not 0,
(2) if y is 0, then x is not 0, and
(3) x + y is greater than 0.001 and less than 1.
; . . . .
.. : . .
. . ~,
.
' . :
~32~7~
F-4690(4765) --5--
In the above composition, the +3 valence element x is
preferably selected from aluminum, iron, chromium, vanadium,
molybdenum, arsenic, antimony, manganese, ~allium and boron; the +4
valence element Z is preferably selected from silicon, germanium and
titanium; the +5 valence element Y is preferably selected from
phosphorous, arsenic, antimony and vanadium. Most preferably, X is
aluminum, Y is phosphorus and Z is silicon.
In the composition above, depending on the values of x and
y, the composition can be a cation exchange material with potential
use as an acidic catalyst, or it can be an anion exchange material
with potential use as a basic catalyst.
The composition of the present invention is prepared by
providing a reaction mixture comprising sources of X oxide, Y oxide
and ~ oxide, water, an organic directing agent D, inorganic cations
M and anions N, the components of said reaction mixture having the
following relationship:
( )a (M2o)b (x2o3)c (zo2)d:(y2os)e:(N)g:(H2o)h
where a, b, c, d, e, f, g, and h are numbers satisfying the following
elationships:
~'
~- d/(~+2c+2e) is up to 0.2 (preferably 0.05 to 0.2)
a/(d+2c+2e) is 0.2 to 0.4, and preferably the additional
relationships: b/(c+d+e) is less than 2,
c e
g/~c+d~e) is less than 2, and
h/(c+d~e) is from 3 to 150,
` The initial pH of the reaction mixture should be 4-6. The mixture
is heated with agitation to a temperature of 130 to 155C and
maintained at this temperature until crystals of oxide material are
formed.
The pH is controlled durin~ the reaction so that the final
pH is 6-7 and the reaction to produce at least 70%, and preferably
" ~
,
., . ~ ,:
F-4690(4765) --6-- ~ 3 2 9 7 9
at least ~ of the c~n~osi.tion of the invent.ion (based on tho
~ei~ht o~ the total cry5tal~ine phase) i~ no~nally complete ~fter
4-20 ho~irs. The crystal]ine produc~ i~ recovcred by separating s~nle
from the reactlon n~dilJm, such as by ~ooling th~ whole to room
temperaturel filtering and ~ashing with wat~r before dryin~.
In som~ cases it may bc desirable to employ a t~o-phase
react.ion ~ixture, in which at least one of the X~ Y and Z o~ldes is
dissolved or dispersod in an organi~ solvent.
The ~hove reaction mixture ~on~pos~ion can be prep~red from
~ny suita1~1e malerl~ls whicll su~ply the appropriat~ componcnts.
U~cful sotlrc.es o ~3 v~lenc.e elemcnt, e.~, ~luln;n~lm, include any
known form of o~lde or hydroxide, org~nic or ino~ganic salt or
~ompo~lnd. Useflll sourc.es of 14 valence element, e.g. silicon,
include, any known form of dio~ide or silicic ~cid, alkoxy- or other
co~pounds ~f sueh elclnent. Useful sources of ~5 val.enc~ elernçnt,
e.g. phosphorus~ includc, any ~nown form of phosphorus acid~ or
phosphoru~ o~ides, p~los~hates and phosphites, and organic
der~vatives of sur.h elcment.
The ol~anic. solvent is a C5-C10 alcohol or any oth~r
liqllid co~l~olmd substanti~ly ilr~ cible ~it.h w~ter.
The organic tlirecting ag~:nt ~an be an organic mono- or
dialkylamine, ~ith a~kyl being of 3 or 4 ~arbon atoms, or an onil3m
coln~o~mds having the followin~ for~ula:
R4M X or ~R~l 3 2
wherein R or R' is alkyl of fro~ 1 to 20 carbon atoms, or
~onlhinations thereof; ~1 is a tetr~oordinate e]cment (e.g. nitro~en,
phosphorus, arscni~, antinlony or bisnmth); and X is an anion (e.g.
fluoride, chloride, bromide, iodide, hydroxid~ etate, sulfate,
car~oxylate), Partiell~arly prcferred directing agents inc.lude
tetraethylammonium hydro~de, tetrapro~ylammoniu~ bromide or ~ost
preferably tetrapropylammonillm ~ydroxide and dialkylamines wherein
alkyl is butyl or most prefcrahly prnpyl.
..:.. ,`
~29798
F-4690(4765) --7--
In order to avoid the production of unwanted crystalline
phases, the temperature must be carefully controlled within the 130
- 155C range specified abaove. The preferred temperature within
this range depends on the directing agent employed, so that with
dipropylamine the preferred temperature is 135 - 155C, most
preferably about 150C, whereas with tetrapro wlammonium hydroxide
the preferred temperature is 130 - 145C, preferably about 135C.
In its synthesized form the present composition will also
contain occluded organic directing agent and water molecules,
entrapped during the synthesis and filling the microporous voids.
; However, these can be removed by heating.
The original cations of the as-synthesized present
composition can be replaced in accordance with techniques well known
in the art, at least in part, by ion exchange with other cations.
~ 15 Preferred replacing cations include metal ions, hydrogen ions,
; hydrogen precursor, e.g. ammonium, ions and mixtures thereof.
Particularly preferred cations are those which render the
composition catalytically active or control catalytic activity,
especially for hydrocarbon conversion. These include hydrogen, rare
earth metal and metals of Groups IA, I~A, IIIA, IVA, IB, IIB, III~,
IVB, VIB and VIII of the Periodic Table of the Elements.
~ A typical ion exchange technique would be to contact the
`j synthetic present composition with a salt of the desired replacing
cation or cations. Examples of such salts include the halides, e.g.
chlorides, nitrates and sulfates.
` The crystalline composition of the present invention can be
`~ beneficially thermally treated, either before or after ion
exchange. This thermal treatment is performed by heating the
1 composition in an atmosphere such as air, nitrogen, hydrogen, steam,
etc., at a temperature of from 300C to 1100C, preferably from
350C to 750C, for from 1 minute to 20 hours. While subatmospheric
: or superatmospheric pressures may be used for this thermal
treatment, atmospheric pressure is desired for reasons of
convenience.
~3297~8
F-4690(4765) --8--
.~
It may be desirable to incorporate the new composition with
another material, i.e. a matrix, resistant to the temperatures and
other conditions employed in various organic conversion processes.
Such materials include active and inactive material and synthetic or
naturally occurring zeolites as well as inorganic materials such as
clays, silica and/or metal oxides, e.g. alumina. The latter may be
either naturally occurring or in the form of gelatinous precipitates
or gels including mixtures of silica and metal oxides. Catalyst
compositions containing the present composition will generally
comprise from 1% to 90~ by weight of the present composition and
from 10% to 99~ by weight of the matrix material. More preferably,
; such catalyst compositions will comprise from 2~ to 80% by weight of
the present composition and from 20% to 98~ by weight of the matrix.
Use of a material in conjunction hith the new composition,
; 15 i.e. combined therewith, which is active, tends to alter the
conversion and/or selectivity of the overall catalyst in certain
organic conversion processes. Inactive materials suitably serve as
diluents to control the amount of conversion in a given process so
that products can be obtained economically and orderly without
employing other means for controlling the rate of reaction. These
materials may be incorporated into naturally occurring clays, e.g.
bentonite and kaolin, to improve the crush strength of the catalyst
~.;
under commercial operating conditions. Said materials, i.e. clays,
oxides, etc., function as binders for the catalyst. It may be
desirable to provide a catalyst having good crush strength because
in commercial use it is desirable to prevent the catalyst from
breaking down into powder-like materials. These clay binders have
been employed normally only for the purpose of improving the crush
strength of the overall catalyst.
` 30 Naturally occurring clays which can be composited with the
new crystal include the montmorillonite and kaolin families which
include the subbentonites, and the kaolins commonly known as Dixie,
McNamee, Georgia and Florida clays or others in which the main
mineral constituent is halloysite, kaolinite, dickite, nacrite, or
1~297~
F-4690(4765) --9--
anauxite. Such clays can be used in the raw state as originally
mined or initially subjected to calcination, acid treatment or
chemical modification.
In addition to the foregoing materials, the present
composition can be composited with a porous matrix material such as
aluminum phosphate, silica-alumina, silica-magnesi~,
silica-zirconia, silica-thoria, silica-beryllia~ silica-titania as
well as ternary compositions such as silica-alumina-thoria,
silica-alumina-zirconia silica-alumina-magnesia and
silica-magnesia-zirconia. The relative proportions of finely
; divided crystalline material and inorganic oxide gel matrix vary
widely, with the crystal content ranging from 1 to 90 percent by
weight and more usually, particularly when the composite is prepared
in the form of beads, in the range of 2 to 80 weight percent of the
composite.
Employing a catalytically active form of the present
composition as a catalyst component, said catalyst possibly
containing additional hydrogenation components, reforming stocks can
j be reformed employing a temperature of 370C to 540C, a pressure of
100 psig to ~000 psig (791 to 6996 kPa), preferably from 200 psi~ to
700 psig (1480 to 4928 kPa), a liquid hourly space velocity is of
0.1 to 10, preferably 0.5 to 4, and a hydrogen to hydrocarbon mole
ratio of 1 to 20, preferably 4 to 12.
A catalyst comprising the present composition can also be
used for hydroisomerization of normal paraffins, when provided with
a hydrogenation component, e.g. platinum. Such hydroisomerization
is carried out at a temperature of 90C to 375C, preferably 145C
' to 290C, with a liquid hourly space velocity of 0.01 to 2,
preferably 0.25 to 0.50, and with a hydrogen to hydrocarbon mole
ratio of 1:1 to 5:1. Additionally, such a catalyst can be used for
olefin or aromatic isomerization, employing a temperature of 200C
to 480C.
~'
- . :, . .. . . . .
' '. ' ~: '
, ' .
- -
F-4690(4765) --10-- 1 3 2 9 7 9 8
~ uch ~ cata~yst c.~n a3so be ~sed for redueing th~ poUr
poi~t of gas oi~s. l~is re~c.tion i~ carried out at a liquld hourly
space velocity o 10 to 30 alld at a temperature o~ 425G to 59~C.
Other reac.t;ons which can be a~complislled ~mploying ~
catalyst ~omprising the composition of this inYen~ion containin~ a
metal, e.g. platinum, include hy~rogen~tion-dehydrogenation
reacti~s and dçsulLurjzation reactions9 olef;n polymerization
(o~igomeriz~tion) and ot}ler or~anic conlpolmd conversions~ s~ch as
the conYersion o~ alGohol~ (e.g. methanol) or eth~rs (e.g.
dimethylether~ to hydroc~rbons, and the ~Ikylation of arornati~s
(e.g. ben~ene) in the presence of an alkylati~ agent (e.g.
etllylenc)~
The invent;on wi]l now bc more part;cularly described ~i~h
reEcrence to the ~xamples and the acc.on1panying drawin~s, in which:
Fi~re 1 sh~ws the X-r~y diffraction patt~rn of the
as-synthe$ized Example 1 product;
Fi~ure 2 sho~s the X-ray diffractlon pattern o~ the
calcined Px~ple 1 ~rodu~ nd
~ lgure 3 s}l~ws the X-r~y diffra~ion p~ttern of the
as-synthesi~d ~xample 3 product; and
Figure 4 shows the X-r~y diffraction pattern o~ the
~lcincd F.x~nlple ~ pr~luct.
AMP~ 1
A two-phase syn~hcsis r~action mixture wa~ prepared wlth
the org~nic phase ~olnprisin~ ~Og Si ~OC2~5)4 and 60g
l-h~x~nol, ~n~ th~ aqueou.S ph~se comprising 23g H3~04 ~85%), 14g
~1203, l~g d~-n-~ropy~amine (DP~) an~ 60g o~ H20. Thc
. reaction mixture as a whole had t~e ollowin~ approximate
composition:
~ Si/Si~ P - 0.1
`~ DPA/Si~Al~P - 0.2
F-4690t476$) ~ 3 2 ~
l~le reaction mi~ture had a startiTl~ p~ of 5,5 and having
been stirred without he~ting for lS minutes, was hea~cd at 5ûC p~r
hour to 150C and ma~nta;ned at that ~emperatur~ for 24 hours whilc
b~ing stirrcd at 800 rpn until crys~.als of silic.ophosphoaluminate
fornK~d. Thc final pH was 7.
Ihe ~ryst~lline product was scparated from thc reacti.on
nixture by filtration, washed with tolllen~ and ether and then
dried. A s~n~plc of ~he product was then su~lnittcd for X-ray
analysis and found to ~e a crystalline composition exhihiting ~he
dîffraction lines shown in Tal-~e 2A. ~e X-ray dirfraction pattern
of this sampl~: is shown in Fi~ure 1. ~is product, ~fter
ca~cinatio~ ~ 450C in nitro~en and ~ir for four hours each, ~ras
fo~md to have the ~-ray pattern shown in T~ble 2~ and ~gure 2.
~-46~0(4765) --12--I 3 ~ :~ 7 ~ ~
Tabl.e ~A
Int~rplanar ~bscrve~dRelative Intensities
d-~ac;n~ (A~ ~ x l~ota _~_
* 16,3 5,4~ lO0
lO.B 8 15 2
* 8 18 10.81 10
6 68 13~24
5 64ll4 31 4
* 5.46 16.24
4.g3317.98
4 B42l8 32 2
~, 2'~622o 45 2
4.08~Z1.74 7
* 4.~572l.gO
3,82823. 23 3
~* 3.636~4,47
3.5gO~4.86
* ~.41926.06
* 3.3~6Z6.24
3 37028 26 6
3 08~2~.9~ 3
3 .0~92~. 4~ l
*diffrac~ion lines identiying a c.rystal framework
topo~ogy having pore windo~s formed by 18 tetrahedral
~emhe~ s .
~diffrac.tion lines of * plus additional intensity
contri~ution fro~ oth~r crysta11ine ~ihase.
**~ douhlet.
'' ., ~ '
.
,
F-46~0(~1765) --13-- 13 2 ~ 7 ~ 8
T~l e 2~
~b r ed ~elat1ve Intensities
Interpl~nar ~e v III
d~S~ac.in~ (A~ ~ _ Q _ 7,
* 15,4 5,37 lOn
3-4 8.2
3.2l 10 78 14
4,917 ~8,0
~,092 21.71
3 ~65 22 ~11 6
3 ~34 23 lg
** 3 767 23,61
3.6fJ8 24.Z6
3~633 2~.50
3 581 ~4.R6
3 405 266 04
~ 365 ~6.48
3,328 26 7~ 1
~ 3 ~77 27.20 9
3 054 2a.2
*dif~raction lin~s identifyin~ a crysta~ fTam~:~4r~
topology having pore windows formed by 38 tetrahedral
m~mbers .
**diffraction ~inoS of * plus additional intensity
çontrlbl~tinn froln other crystal~ ine pl ase.
~** douhlet.
.
~ , ~ .. . . .
: : ~ , . . . .
.
~ ' .: ' ''
~3297~
F~4690(4765) --14--
Analysis of the X-ray data of the as-synthesized and
calcined products showed the the crystalline phase contained in
excess of 80% by weight of the crystalline material of the invention
having the X-ray lines listed in Tables 1~ and lBo
EXAMPLE 2
The process of Example 1 was repeated but with the reaction
mixture being heated at 50C/hour to 130C, maintained at this
temperature for 24 hours, heated to 200~C, and then maintained at
this temperature for 24 hours. In this case, although the
composition having the X-ray lines listed in Tables lA and B was
present, it constituted less than 70% by ~eight of the overall
crystalline product.
Ex~ple 3
A mixture containing 38.3 g of 85~ orthophosphoric acid
(H3P04) in 50 g water was mixed with 22.97 g hydrated aluminium
oxide (Kaiser A1203). The mixture was heated to 80C with
i stirring for 1/2 hour. To this mixture was added 108.8 g
; 20 tetrapropylammonium hydroxide (TPAO~ 25%). Crystallization in an
autoclave was at 135C at autogenous pressure for 16 hours. The
solid product was filtered, washed and dried. Figure 3 shows the
X-ray diffraction pattern of the as-synthesized material and Figure
4 shows that of the calcined material (calcined at 53~C in N2 for
2 hours). Tables 3 and 4 show X-ray powder diffraction data of the
as-synthesized and calcined samples, respectively.
Analysis of the X-ray information indicated that the
crystalline product of this example contained in excess of 90% by
weight of a material having the X-ray lines of Tables 1~ and lB.
' , , , :, : ~ : .
F-4690(4765) --15-- 13 %
Tal)le 3
~nterpl~nar ~bservcd R~lative
d-Spacin~s (A~ 2xl~eta Intens1ties (I/I
_
- 16.3 5-43 lûO
13,4 6.5~ 2
12.0 7'3g 4
11.4 7.7~ ~
g.3 9,47 ~l
8.10 10.92 11
6.85 12.92 < 1
6.l5 1~.40
5.~7 14.85 ~ 1
5.3~ 16~44 2
~70 lg.00 5
4. 4~ .75 2
4,3~4 20.2~ 1
q 241 ~0.~4 2
4 143 Z].45 g
4.0~6 ~1,86 10
4.014 22.15 8
3.946 22 . 53 10
3.707 24,01 10
3.531 25 . 22
3.~31 ~5.97 2
3 ~88 26.31
3 Z46 27.47
3. ~04 2% .7~ 3
3.045 2!~,~3
. .
'
..
' ,, ; -
,
~\
F-4690( ~1765 ) - -16 - -
~ 32979~
Tabl e 4
Interplan~ ~bscrved Relative
d-~pacin~s tA) ZxThctaInt~nsities (J/Io)
16.5 5.36 lOn
12.0 7.~58
9~5 9.32
8 . Zl 10 .78 12
6.17 14.35 3
.47 16.~1 ~
4.729 1~.76 5
4.28~ ~),75
4.081 21.78 11
3.959 Z2.~6 8
3.840 23.16
3 . 760 23 . 66 7
3.638 24.46
3~57~ ~4.88 2
3.40g ~6.14
3. ~74 27 . 2~ 8
3.155 28.Z8
~082 2~.97 3
3.Q2g 2g.49
;
.
.~ ..
,
.
,.~
- . .
