1~P6346
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~¦ The present invention relates to novel clay
;I derived co~positions, and more specifically to
interlayered derivatives of smectite type minerals
Ilayered clays) which possess considerable internal
micropore volume and have useful catalytic and adsorbent
~ properties.
¦ Layered naturally occurring and synthetic smectites
~1 such as bentonite, montmorillonites and chlorites may
`~ be visualized as a "sandwich" comprising two outer
layer of silicon tetrahedra and an inner layer of
alumina octahedra. These "sandwiches" or platelets
;1 are stacked one upon the other to yield a clay particle.
~ Normally this yields a repeating structure every nine
`1 20 angstroms or thereabouts. Much work has been done to
demonstrate that these platelets can be separated
¦ further, i.e. interlayered by insertion of various
polar molecules such as water, ethylene glycol, various
amines, etc. and that the platelets can be separated by
as much as 30 to 40A. Furthermore, p-ior workers:', :
similarly prepared phosphated or alumino-phosphated
interlayered clays as low temperature traps for slow
release fertilizer. The interlayered clays thus far
prepared from naturally occurring smectites are~not
suitable for general adsorbent and catalytic applications
', ~ A
` _"
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due to the fact -they tend to collapse when subjccted
~; to high temperatures.
Description of the Prior Art
U.S. patents 3,803,026; 3,844,979; 3,887,454; and
3,892,655 descri~e layered clay-like materials and
the process for using these materials. The layered
clay materials are prepared from synthe-tic solutions
of silica, alumina and magnesia salts. The final
product has a composition similar to the composition
of the clays covered in the instant application. The
product of the instant application differs from the
disclosed products, in that it contains non-exchangeable
alumina between the sandwiches and an interlayer
spaciny greater than aDout 6A is characteristic of an
anhydrous product.
U.S. Patent 3,275,757 also discloses synthetic
layered type silicate materials as does U.S. Patent
3,252,889. U.S. Patent 3,586,478 discloses the method
of producing synthetic swelling clays of the hectorite
type by forming an aqueous slurry from a water soluble
magnesium salt, sodium siIicake, sodium carbonate or
sodium hydroxide ana materials containing lithium and
flouride ions. The slurry is then hydrothermally treated
to crystallize a synthetic clay-like material.
U.S. Patents 3,666,407 and 3,671,1gO describe other
methods of preparing clay~like materials. All of these
i synthetic clays are acceptable raw materials ~or use in
the instant invention in place of the naturally occurring
clays. ~owever, by virtue of ready availability of large
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quantities at low prices, the natural clays will ~enerally
be prepared for use in the present invention.
; U.S. Patents 3,798,177 and 4,060,480 disclose the
preparation of hydroxy-aluminum modified smectite clays
' wherein a gibbsite-like layer is formed between the
crystalline layers of the clay. The gibbsite-like
layer is continuous and does not substantially increase
the internal pore volume (micropore characteristics) of
the modified clay material.
The present invention distinguishes over the prior
~: art in that it is concerned with a novel method for
modifying known smectite type minerals in such a way
as to produce a subs-tantial micropore structure in the
minerals and thereby yield novel catalytic and sorbent
products having utility in the petroleum, cKemical and
related industries. The resultant properties may be
; viewed as being more characteristic of crystalline
zeolites than clays.
srief Description of the Invention
The present invention relates to the preparation
of novel "pïllared" interlayered clays which are obtained
- ~ .
by reacting smectite type clays with polymeric cationic
hydroxy metal complexes. The pillared interlayered
clays-of our invention possess a unique internal micropore
structure which is established by introducing discrete/
non-continuous inorganic oxide particles, i.e. pillars,
.,.,, O
having a length of about 6 to 16A between the clay layers.
; These pillars serve to prop open the clay layers upon
~ removal of water and form an internal interconnected
, ,
micropore structure throughout the interlayer in which
the majority of the pores are less than a~out 30A in
diameter.
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More specifically, we have found that thermally
stable interlayered clays which have an interlayer
spacing of up to about 16A and greater than 50% of
i~s surface area in pores of less than 30A in diameter
may be prepared by reacting a naturally occurring or
synthetic smectite type clay with a polymeric cationic
hydroxy metal complex, such as aluminum chLorohydroxide
complexes ("chlorhydrol"), and heating to convert the
hydrolyzed polymer complex into an inorganic oxide.
Thus, in acco~clance ~ith the present teachings,
an interlayered smectite clay product is provided
which includes an inorganic oxide selected from the
group consisting of alumina, zirconia and mixtures thereof
~etween the layers thereof, and which possesses an inter-
layer distance of from about 6 to 16 A, the interlayered
clay has greater than about 50 percent of its surface
area in pores of less than 30 A in diameter.
.
.~ In accordance ~ith a further emhodiment of the
; present teachings, a process is provided for preparing
: 20 an interlayered smect~te which comprises reacting a smectite
.; with a mixture o~ a polymeric cationic hydroxy inorganic-: metal complex.selected from the group consisting of
aluminum ancl zirconium complexes and mixtures thereof
and water to obtain a smectite having greater than 50
percent of its surface area in pores of less than 30 A
in diameter after dehydration, and separating the inter-
layered smectite from the mtxture.
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A more clear understanding of our invention may
be obtained from the following detailed description,
specific examples, and drawing wherein:
igure 1 represents a cross-sectional view of
the structure of a typical smectite type clay which may
be used to prepare the novel interlayered clay products
, of our invention.
' Figure 2 is a cross-sectional view of the clay of
Figure 1 which has been treated with a polymeric cationic
hydroxy metal complex to form a pillared interlayer
between the clay layers; and
Figure 3 represents the compositian of Figure 2
, which has been calcined to convert the interlayered
polymeric complex into "pillars" of stable inorganic
-; oxide.
`,~, To obtaïn the novel pillared interlayer clay products
~; of our invention the following general procedure may be
' used: ' , ;
1) A smectite clay lS mixed with an aqueous
solution of~a polymeric' cationic hydroxy
~'¦ ' metal complex such as aluminum chlorhydrol,
"~ ' .
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,
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in amounts wherein the weight ratio of clay
to metal complex solution is from 1:2 to
1000. The metal complex solution will
preferably contain from about 1 to 40~ by
weight solids in a suitable liquid medium
such as water.
The mixture of clay and metal complex
is maintained at a temperature of about
5 to 200C for a period of'0.1 to 4.0 hours.
: , . .
3) The reacted clay solids are recovered and
'~ heated at a temperature of from about 200 -'
to 700C to decompose the hydrolyzed metal
com~lex to a pillar of inorganic oxide.
The clays used as starting materials'in the present
' invention are the group of minerals commonly called
.. . . .
smectites an~ represented by the general formula:
(Si8) V(Al4) O20(OH)4
where the IV designation indicates an ion coordinated
to four other ions, 'and VI designates an ion coordinated
to six other ions. The IV coordinated ion is commonly
-Si4+, A13+ and/or Fe3+, but could also include several
other four coordinate ions (e.g., P5 , B3 ,'Ge4+, Be
etc~. The VI coordinated ion is commonly Al or
Mg2+, but could also include many possible hexa-
coordinate ions '(e.g.' Fe3+, Pe2+,~'N12+, Co2 , Li+, etc.).'
The charge cleficiencies created by the various '
substi~utions i~to these four and six coordinate cation
positions, are ~al'ànced'by~one or several'cations ~
3~6
;; located between the structural units. h7ater may also
be occluded between these structural units, bonded
either to the structure itself, or to the cations as
-~ a hydration shell. When dehydrated, the above structural, .
units have a repeat distance of about 9.1 A, measured
by X-ray diffraction. Typical commercially available
clays include montmorillonite, bentonite, beidellite
; and hectorite.
The inorganic metal polymers used in the practice
of the present invention are generally known as basic
aluminum; zirconium, and/or titanium complexes which
are formed by the hydrolysis of aluminum, zirconium,
- and/or titanium salts. While there is some disagreement
on the nature of the species present in hydrolyzed
metal complex solutions (or suspensions), it is generally
- believed that *hese mixtures contain highly charged
`~ cationic complexes with several metal ions being
x complexed.
,~ - The inor~anic aluminum polymers used to prepare
~0 our novel pillared interlayered clay compositions
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-~ comprise solutions of discrete polymer particles having
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i~ a generally spherical shape and a diameter of about 8A
.. . .
~i` and in which the aluminum atoms are present in the- - ; ,
tetrahedral coordinated form to an extent of up to
: about lO~i as determined b~ NMR measurement as shown by
,
;~ Rausch and Bale, in J. Chem. Phys. 40 (11), 3391 (1964),
.: . . . : ........................... . -
the remaincler bei~g octahedral coordinated. The typical
.,j, .
- hydroxy-aluminum polymers previously used to produce
unLform gibbsite; layers ~etween cla~ }ayers,~ is~
characterized~by the presence of substantially 100
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octahedrally coordinated aluminum ln the f orm of gihb
; gibbsite-like sheet polymers.
' When AlC13 6 H20 dissolves in water, it ionizes -
''- as follows: ' '
Al(H20)6 + 3Cl
with most o,f theiCl being ionic. Since such solutions
are acidic, then hydrolysis must take place to a
substantial degree, particularly in,view of the
, relatively high value of the ratio of ionic charge to
"~ 10 ionic radius which characterizes the aluminum ion. The
~,~ initial hydrolysis step is
,~ Al(H20~6 ~ [Al(H~0)501I] ~ H
and the complex ion formed by this hydrolysis is basic.
~ In the usual terminology of such complexes, this
,~ hydrolysis product is "1/3 basic". Such a species is
, present in acidic aluminum chloride solutions, since
'~ hydrolysis is responsihle for the acidity of these
solutions. , ,
, . . .
: As a means of better understanding these basic
~` 20 polymers, it is important to differentiate between
' the basicity of a solution and the basicity of a complex
. - . . : . ,
; ' ion in solution. The nature of the polymer species
-- present is dependent on pH, concentration and temperature.
~;~ ' Lowering-the pH by addition of H~ shifts the hydrolysis
, reaction to the le~t, causing a decrease in the average ,
molecular weight of the polymer. It is important to '
~ note that thé total basicity o~ the complexes will
,~ always~be greater than the basic,ity of the solution per ~'
se, because o the factor of hydrolysis. Increasing
concentration and higher,temperatures fàvor incrèased,~
.~
63~f~
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degrees of hydrolysis, leading to larger polymers.
The hydrolysis of cations brings about polymers
through a process called olatIon, which is described
by C. L. Rollinson in Chemistry of the Coordination
.:
Compounds, Edited by J. C. Bailar, Reinhold Publishing
'- Corporation, New York, 1956, as follows:
- _ ++ _ _ ++ H 1 +4
(H20)4Al Al(H2)4 > (H20)4Al\ / l(H20)4 + 2 H20
OH2 HO _ H _ ,
In this process single or double OH bridges can be formed
between ~1 ions. In less acidic solution, larger
,' polymers are formed by the process and the bridying OH
,- can be converted to bridging o 2, a process called
~ oxolation. Note that a doubly OH bridged complex is
'~ a pair of edge-sharing octahedra, and this is the s-ame
.
type of structure found in boehmite, AlOOH, where the OH
groups at the surface of the layers are each shared between
two A106 octahedra. In hydrargillite, Al(,OH)3, all
` oxygens are also shared between two A106 octahedra.
,, Some of the prior art methods that have been used
' to prepare Al polymers include:
, al Tsutida and Kobayashi: J. Chem. Soc. Japan (,Pure
Chem. Sec.l, 64, 1268 (,1943) discloses the reaction
of solutions of AlC13-6 H20 or HCl with an excess
- of metallic aluminum;
nAl+2AlX3 ~ A12+n~OH)3nX6
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b) Inove, Osugi and Kanaya; J. Chem. Soc. Japan
(Ind. Chem. Sec.~, 61, 4Q7 (:19581
discloses that more than an equivalent amount of
aluminium hydroYide :is reacted with an acid;
2~nAl(OH~3~6HX ~ A12~n(OH)3nX6
c) H. ~. Kohlschuter et al.: Z. Anorg. Allgem. Chem~,
248, 31Y ~1941~ desc:ribes a method wherein alkali
is added to an aluminum salt solution;
2~nAlX3+3nMOH ~ A12~n(OH~3n~6
d~ T. G. Owe Berg: Z. Anory. Allgem. Chem., 269
213 (1952) discloses a procedure wherein an
aqueous solution of AlX3 is passed through
an ion exchange column in OH form, and
el R. Brun: German Patent ~ 1,102,713 describes
extended heating at~ 150C. of salts such as
AlC13 6H2
The inorganic aluminum polymers used in the
practice of the present invention are visualized
~; as having the general formula:
A12~n (OH~3n ~ 6
wherein n has a value of about 4 to 12; and X is
usually Cl, Br, and/or NO3. These inorganic metal
polymers are believed to have an average molecular
weight of from about 300 to 3,000.
In addition to the above described aluminum
complex polymers, polymeric cationic hydroxy complexes
of metals such as zirconium, titanium, and mixtures
thereof may be used. Preparation and description of
zirconium complexes are described in:
.~ -- 10. --
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1) A. Clear~ield and P. ~. Vaughan, Acta Cryst. 9,
555 (-1956);
21 A. N. Ermakov, I. N. Marov, and V. K. ~elyaeva,
Zh. Neorgan. Khim. 8 (7), 1623 (1963~.
3~ G. M. Muha and P. A. Vaughan, J. Chem. Phys.
33, 194-9, (1960~.
It is also contemplated that copolymers of the above
noted metal complexes with silica and magnesium may be
used. Furthermore, it is contemplated -that the
hydrated or dehydrated metal complex treated smectite
~^ clays may be post treated with solutions of silicate,
~`~ ~agnesium, and phosphate ionis to obtain moxe stable
and attrition resistant compositions.
The catalytic and adsorbent characteristics of
the interlayered smectite clays of the present invention
may be modified by ion exchange with a wide variation
of cations including hydrogen, ammonium, and metals of
Groups IB through VIII of the periodic table. In
`; particular catalytic cracking and hydrocracking catalysts
which contaIn rare earth, cobalt, molybdenum, nickel,
tungsten, and/or noble metal ions are active for the
catalytic conversion of hydrocarbons.
Referring to the drawing, Figure 1 represents
a typical smectite wherein the layers or platelets
O
have a repeat distance dl of about 9 to 12A depending
on the degree of hydration. As shown in Figure 2,
;~ smectites which have ~een treated with metal complex
polymers in accordance with the teachings of the present
invention, have an increased repeat distance of d2 of
from about 16 to about 24A. In Figure 3, a platelet
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repeat distance d3 which is less than d2 is shown in
exaggerated form. The repeat distance d3, which is
esta~lished when the pïllared metal complex polymer
i`nserted between the platelets is decomposed by
calcination to temperatures of about 200 to 700C.,
is found in practice to be substantially the same as
d2, with only minor shrinkage of the pillared layer
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occurring to the extent o less than 0.5 A in
cases. All the distances dl, d2 and d3 (layer repeat
distances) are readily obtained directly from the
X-ray diffraction patterns of the various products,
and represent the first-order basal reflection
parameter (i.e. 001~. The "interlayer distances" are
obtained by subtracting the thickness (about 9A~ of
the clay layer from the basal spacing obtained by
X-ray diffraction, i.e. d4 = dl-9; d5 = d2-9; and
d6 = d3-9-
Recent research on the clay minerals has shown
that within a given clay structure the layers are not
uniform, but form a heterogenous chemical mixture in
which the exact composition of one layer may be somewhat
different from that of an adjacent layer. This would
be expected to result in slight variations in charge
between layers, and therefore, slight differences in
i the amount of polymer exchanged in different layers. As
. . the size of the polymer is the controlling factor in
setting the interlayer dis-tance, charge heterogeneity
on the layers would only effect the number of polymer
species between the layers (i.e. the number of resultant
3Q pillars, not their size).
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In general, the ealeined produets of our invention
will have an interlayer spaci`ng of about 6 to 16A, a
nitrogen sET surface area o~ about 150 to 600 m /g,
and a nitrogen pore volume of ahout 0.1 to about 0.6
ee/g. Furthermore, our novel pillared interlavered
. elay eompositions possess a substantial internal
mieropore structure which is characterized by a pore-
size distribution in whieh more than 50%, and in many
eases more than 75% oE the surfaee area is located in
pores less than 30A in diameter as determined by
.
eonventional nitrogen pore size distribution (PSD)
adsorbtion measurements. The conventional prior art
gibbsite-like interlayered elay produets (synthetie
ehlorites~ possess no substantial surfaee area in pores
. O
less than 3QA in diameter.
Our interlayer produets are useful as adsorbents
and eatalytic supports. Furthermore, it is eontemplated
that our interlayered elay products may be combined
~ith other inorganic oxide adsorbents and catalysts
;; 20 sueh as siliea, alumina, siliea-magnesia, siliea-
alumina hydrogel, and natural or synthetie zeolites,
and elays. Our produets are partieularly useful in the
preparation of eatalysts whieh eontain aetive/stabilizing
metals sueh as platinum, palladium, eobalt, molybdenum,
niekel, tungsten, rare-earths and so forth, as well as
matrix eomponents such as silica, aluminum and silica-
alumina hydrogel. These catalysts are used in
conventional petroleum conversion processes such as
catalytic craeking, hydrocracking, hydrotreating,
30 is-omerization and reformi`ng catalysts; and as molecular
sieve adsorbents.
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a~ing descri~ed the ~asic aspects of our lnvention,
the followïng speci~ic examples are ~iven to illustrate
preferred specific embodiments.
Example_l
A clay slurry was prepaxed from the natural clay
product designated Volclay~ 200 by American Colloid Co.
A total of 32,000 ml. of a clay slurry containing 2.7
percent solids and an aluminum chlorohydroxide solution,
prepared to contain 50 weight percent of the salt, and
1,110 grams of this solution was added. The resulting
mixture was aged for one half-hour with agitation and
the temperature was increased to 160. The slurry was
aged for 1/2 hour at this temperature, the product
was filtered, washed once with 16 gallons of hot
; deionized water, reslurried in deionized water and spray
drïed. The properties of the product are set out in
Table 1.
Example 2
;A total of 31.7 gallons of the less than or equal
to 2 mïcron sized particles of the natural clay product
designated Volclay~ 200 by American Colloid Corporation
was prepared by centrifugatïon. A 50 weïght percent
solutïon of aluminum chlorohydroxide was prepared and
6,920 grams of the resulting solution was added to
the clay slurry. The slurry was aged for 1/2 hour at
160F. and filtered on a belt filter. The filter cake
was reslurried ïn deionîzed water; refiltered and again
reslurried ïn deionized water and spray dried. The
. . .
properties of the interlayered clay product are set out
in Table 1 below.
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The catalytic activi.ties of th.ese products were
determIned using the microacti`vity -test described
i`n the article by F. T. Cîapetta e-t al. in the Oil
and Gas Journal of October 16, 1967. The feed stock
was a West Texas gas oil boiling in th.e range of 500
to 8QQF. The reactor was operated at a temperature
of 92QF., a weight hourly space velocity of 16 and
had a catalyst/oil ratio of 3. The product of Ex~mple 1
gave a 98.6% conversion, and the product of Example 2
gave a conversion of 82.5%.
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, Example 3
One of the problems in encountered in the preparation
, of thes-e slurries where the particle size is equal to or
.. less than 2 microns is the tendency to loose part of the
;, product through the fïlter. To combat this problem a
`,' flocculating agent was added to the clay slurry.
A batch of interlayered clay was prepared in Example 1.
Varying amounts of a high molecular weight GUAR designated
polymer 7050-B by Stein, Hall & Co. were added to portions
of the clay slurry. Each. sample was filtered on both a
coarse (2-3 cubic eet/minute~ and a fine (1 cfm) filter
, cloth. Results from the 0.5 to 10 grams polymer/100 grams
clay indicated thickening at all levels, but 1 to 3 grams/100
~': grams appeared to yield the clearest filtrates. When slurries
,~ were prepared without a flocculating agent, a considerable
.'., amount of product was lost through the coarse filter cloth.
, . .
. The flocculations can also be affected by an addition
.,. ~
"~, of low levels of sodium silicate (0.5 grams SiO2/100 grams
.,: clay~. There was little 105S in product surface area with
' 20 th.ï.s treatment. Other flocculating agents of the anionic
,.,,~ of neutral type would be equally effectïve~
Example 4
'~j This example illustrates the use of calcium
,~. bentonite as the raw material in our novel process.
,', A slurry of particles having a particle size of
equal to or less than 2 microns of calcium bentonite
furnished by American Colloid Corporation was prepared
hy centrïfugation. A total of 26.7 grams (:dry basis), of
clay- from th.is s:lurry was diluted to 5.4 1. and 38.0 grams
of a 50 weïgh,t percent aluminum chlorhydroxide solution
was- added. The slurry was aged for 1/2 hour at 25C., and
`~ ' ``
46
the pH was then adjusted to 2.0 with a 3.75% hydrochlor;c
acid solution~ The slurry was- then aged for 1/2 hour at a
temperature of 160F., filtered, washed with 2.7 1. of
hot deionized water and oven dri`ed. The product recovered
had a surface area of 35Q m2~gm. and a (001) basal
spacing of 17.5A.
Example 5
This example illustrates the use of beidellite
clay as a raw material.
A slurry was prepared from 15 grams (dry basis) of
beidellite clay from Taiwan having a particle size of
equal to or less -than 2 microns. The particles
having a particle size of equal to or less than 2 microns
were recovered by centrifugation. A total of 15 grams
(dry basis) of the clay was diluted to 3 liters and
15.1 grams of a 50 wèight percent aluminum chlorhydroxide
solution was added. The resulting slurry was aged for a
, . . ~ .
` period of 1/2 hour. The pH ~as adjusted to 2.0 with 3.75
percent hydrochloric acid solution. The temperature was
increased to 160F. and the slurry was aged at this
temperature for a period of 1/2 hour. The slurry was
filtered, washed with 1 liter of hot deionized water and
i oven dried. The surface area of the product was 307 m /gm.
and the ~001) basal spacing was 18.OA.
Example 6
This example illustrates a method of utilizing
a beneficiatecl montmorillonite without the necessity
of separating the particles that have a particle
size equal to or less than 2 mïcrons. The us-e of
3~ such readily availahle commerci`al product greatly
reduces the pre-processing needed to prepare the
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materials of -this invention. ~ 25 gram. (dry basis)
sample of a higfi purity air-floated Wyomi`ng bentonite
furni`shed by American Colloid Company ~#325 Bentonite~
was slurried in a blender wï.th 1 liter of deionized
water for 1/2 minute. A total of 21.5 grams of
a 5Q percent aluminum chlorohydr.oxide solution was
added and the slurry was aged for 1/2 hour at 150F.
.:
. The ~roduct was filtered, washed with 1 liter of
: hot deionized water, and oven dried at 110C. The
, :
.. 10 surface area of this product was 308 m2/gm.
xample 7
This example i.llustrates the product distribution
`~ o~ a typical product prepared from the product described
~ in Examples 1 and 2. The catalystic activity of the
;.' product was determined using the micro-activity test
~ described in the article by F. G. Ciapetta et al. in
: the Oîl and Gas Journal of October 16, 1967. The
`~ feed stock was a Wes.t Texas gas oil boiling in the
range of 500 to 800F. The reactor was operated at
a temperature of 920F., a weight hourly space velocity
~ of 16 and a catalyst/oil ratio of 3. The test was
carried out after the catalysts had been exposed to a
. temperature of 1000F. for a period of 3 hours. The
data collected in this run is set out in Table II below.
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Table II
Pillared Interlayered
Clay prepared from
Conversi`on Volclay 200
Conv.,* V% 77 3
H2 ,** W% .27
Cl ~ W% . 90
C2=, W% .71
C2 ~ W% .94
Total C3, W% 5~7
Total Dry Gas, W% 8.5
C3=,V% 5.4
C3, V% 4.2
Total C3, V% 9.6
.:
C4=, V% 2.6
iso~C4, V% 8.0
,~ normal-C4,V% 1.7
Total C4, V% 12.3
C4~gasoline., V% 66.9
C5~gasoline, V% 54.6
Coke on cat,, W% 4~5
Coke-Total feed, W% 12.8
.~
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*V% = Volume percent
**W% = Weight percent
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Example 8
It has been found that i`~ the clay was added to
~` the alumi`num chlorohydroxide solution a larger solids
concentration could he affected. Such additions
to the aluminum chlorAydroxide soluti`on may be as high
as abou-t 40 weight percent clay without encountering
problems ;n mixing, pumping, or handling the clay in
the fluid state. This greatly enhances the economy
of the process in that much larger volumes of the
~roduct can be obtaïned and processed in a given time
for a given sized system. The addition of clay to water
followed by aluminum chlorhydroxide addition does not
allow high solids levels to ~e achïeved. The
former process is presumably achieved hecause-the
polymer is instantaneously ïntercallated by the
~,~
clay-as the clay is added, and so inhibits dispersion
of the clay platelets and subsequent formation of
a clay-water gel.
A further advantage is that high solids cut down
the use of energy in the drying step.
In an illustration of this, a total of 2,470
grams of a 50 weight percent of aluminum chlorhydroxide
solution was diluted to 22.7 liters. ~ total of 5,320
; yrams (5,072 gram dry basis) of bentonite was added
to the slurry-. The slurry was aged at ~50~F. for a
period of 1 hour and spray dried. The solids concen-
tration of the product ~ed to the spray drier was
approximately 2a percent, the product re~overed had
a surface area of 273 m ~gm and a lattice d spacing
(001~ of 17.9.
- 21 -
:.
.
Example 9
In thi`s example a slurry containi`ng 15.9 percent
solids was prepared by diluting 2,720 grams of aluminum
.
chlorhydroxide to 6 gallons- and 5000 grams (~dry basis)
- of the clay was added -to this slurry. The slurry
was ag;tated and aged 1/2 hour at 150E'., filtered,
and washed on the filter with 6 gallons of hot deionized
~ater. The product was reslurried and spray dried.
The surface area of the product recovered a 316 m2/gm and
the d spaciny (Q01~ was 18A.
Example 10
' In this example a slurry containing a 35 percent
total solids was prepared by addition of 125 grams (dry
basis~ #325 sentonite clay (American Colloid Co.) to
~ a solution containing 65.2 grams of the aluminum polymer
; in a total volume of 25a ml. This slurry was aged
1 hour at 150F., filtered, washed wîth 1/2 1. hot
~; deionïzed water and dried. The product surface area
was 263 m2/gm. and the (~alJ d spac;ng was 17.6A.
Example 11
In this example a less basic Al polymer is used
;~ to interlayer the smectite. Ordinary aluminum chlor-
.,
hy-droxide (chlorhydrol) contains 5 OH /2 Al 3, and is
5/6 basic. 10 gms. dry basis of 2.0 Volclay~ 200
(American Colloid Co.) as a slurry was diluted to 1.0
1., and ~.3Q gms~ of a 2/3 ~asic Al polymer (i.e.,
- 4 OH ~2 Al 3~ solution contaïning lq.2% A12O3 was
added. This polymer solution was prepared by refluxing
an AlC13.6 H2O solution ïn the presence of excess
aluminum metal until pH 2.8 was- reached. The above
slurry was hot aged 1/2 hour at 150F, filtered,
- 22 -
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. ~-
i . .. ~
:
63~i
,................................. .
...
; washed 2X with 1/2 1. hot deionized water and oven
dried. The interlayered product had a surface area of
286 m2/gm. and a basal spacing of 17.lA.
Example 12
This example indicates that smectites can be
interlayered with Al polymer prepared Erom dehydrated
AlC13 6 ~12O. 9.1 gms. of AlC13 6 H2O was weighe~ in
an evaporating dish, the dish placed in a muffle furnace
set at 325F for one hour and the temperature then
increased to 500F. The sample was withdrawn from the
furnace after a 45~ weight loss. The salt was then added
to 200 ml. of deionized water, 12.5 gms. dry basis of
#325 Bentonite ~American Colloid Co.) was added, the slurry
hot aged 1 hour at 150F, filtered, washed 2X with 250 ml.
hot dionized water and dried at 250F. This sample
had a surface area of 281 m2/gm. and a basal spacing
of 17.7 A.
Example 13
In this example a mixture of AlC13 6 H2O and
~gC12 6 H2O are dried at 250F for 18 hours to a 48~
~ ~eight loss to produce a mixed Al-Mg polymer for inter-
;; layering smectite. 7.6 gms. AlC13 6 ~2 and 2.54 gams.
.
MgC12-H2O were dissolved in 25 ml. deionized water and
then dried at 25QF for 18 hours. The dried salt mixture
was dissolved in 25Q ml. deionized water, 12.5 gms. dry
` ~asis ~325 Bentonite added, the slurry hot aged 1 hourat 15~F, filtered, washed 2X with 250 ml. hot deionized
~ater and dried at 250F. The interlayered clay product
had a surface area of 254 m2~gm. and a basal spacing
of 17.7 A.
- 23 -
.
,
Example 14
This example shows how a well interlayered smectite
can ~e produced from ZrOC124 H2O dried at 500F. 11
~r' gms. of ZrOC12 4 H2O was dried at 500F to a 11~ weight loss, dissolved in 200 ml. deïonized water, 12.5 gms.
dry basis #325 Bentonite added, the slurry hot aged 1
~; hour at 150F, filtered, washed 2X with 200 ml. hot
deionized water and dried at 250r'F. The interlayered
clay had a surface area of 262 m2/ym. and a basal spacing
of 18.8 A.
Example 15
This example shows that interlayering of smectite
can ~e accomplished at elevated temperature and
;~ pressure. 13.6 gms. chlorhydrol (Reheis Chemical Co.)
-~ was diluted to 200 ml. with deionized water, 25 gms.
dry basis #325 Bentonite added and the slurry boiled
1 hour. 20~ of the above slurry was added to a
Hoke high pressure cylinder and aged 1 1/2 houxs at 150C.
The interlayered clay product was then filtered, washed
2X with 250 ml. hot deionized water and oven dried. The
product had a surface area of 279 m /gm. and a basal
; spacing of 17.7A.
`~ Example 16
This example indicates that interlayered smectites
prepared by chlorhydrol ~ Mg~2 coexchange are more
hydrothermally stable than those prepared with chlorhydrol
exchange alone. 54.~ gms. chlorhydrol was diluted to 1.6 1.
; and then 400 ml. of a solution containing 40.8 gms.
. ~
MgC12 6 H2O was added and the mixture aged 3 day at
room temperature. 100 gms. dry basis of ~325 Bentonite
~ was added, the slurry hot aged 1 hour at 160F, ~iltered,
!., 24
~.`' - .
. ~ .
6~6
:,
. .
washed 2X with 1.0 l. hot deionized water and oven dried.
As indicated E~elow, this preparation maintained a greater
deyree of surface area after a 6 hour, 1400F,
atmosphere steam tratmen t than smectite interlayered
with chlorhyarol alone.
Surface Area
Interlayering Species 1-1000F. 6-i4000F, ~ Atm.
Chlorhydrol 270 20
Chlorhydrol + Mg~2 31Q 104
Example 17
This example indicates that reflexed ZrOC12 4
H2O solutions are effective in interlayering smectite.
0.33 M ZrOC12 4 H2O was reflexed for 24 hours and
then 120 ml. of this solution was diluted to 500 ml.,
10 gms. dry basis HPM-20 ~American Colloid Co.~
added, aged 1/2 hour at room temperature~ filtered,
washed 2X with 1/2 1. hot deionized water and oven
dried. The interlayered product had a surface area
of 288 m2/gm and a basal spacing of 22.QA.
Example 18
This example shows that ZrOC12 4 ~I2O solutions
treated with Na2CO3 can effectively interlayer smectites.
125 gms. ZrOC12 4 H2O was dissolved in 1/2 1. solution.
To this solution was added dropwise 1/2 1. of solution
containing 26.5 gms. Na2CO3. After aging for 24 hours,
5~ ml. of the above solution was diluted to l/2 1.,
lQ gms. dry basis HPM-2Q added, the slurry hot aged
1/2 hour at 150F, filtered, washed 2X with 1/2 1. hot
-; deionized water and oven dried. The product had a
30 surface area of 3a9 m2/gm. and a basal spacing of 17.4A.
-- 25 --
:- . , "
.
:.
1~ 4~
.,
Example 19
This example shc~s how CO2 treated ZrOC12 4 H2O
- solutions can effectIvely-interlayer smectite. 125 gms.
of ZrOC12 4 H2O was dissolved in 1,000 ml. deionized water.
C2 (gas) was bubbled through the solution for 2 hours,
and the solution ages 24 hours at room temperature.
5Q ml. of this solution was then diluted to 1/2 1.,
10 gms. dry basis HPM-20 (American Colloid Co.) was added,
the slurry hot aged 1/2 hours at 150F, filtered, washed
10 2X with 1/2 1. hot deionized water and oven dried. The
interlayered clay had a surface area of 279 m2/gm. and a
basal spacing of 16.8A.
Example 20
- This example shows that diluted chlorhydrol when
refluxed, gives interlayered smectites with improved
hydrothermal stability relative to non-refluxed
chlorhydrol. 217 gms. chlorhydrol was diluted to 1.0 1.,
yielding a solution which is 0.5 M as A12O3. This
solution was refluxed for 96 hours. 87.6 ml. of this
20 solution was diluted to 400 ml., 25 gms. dry basis #325
Bentonite added, the slurry boiled 1 hour, filtered,
--~ washed 2X with 1/2 1. hot deionized water and oven dried.
As indicated below, this preparation had a greater
;~ retention of surface area than an interlayered clay
prepared with ordinary chlorhydrol.
Surface Area
Inter_ayering Species 1-1000F. 6-1400F., 1 Atm.
'~ Chlorhydrol 270 20
Refluxed diluted
chlorhy`drol 271 82
, . .
,.
- 26 -
:
." . . . . :
: . .
:
Example 21
This example shows that treatment with SiO3 2 of
either diluted refluxed chlorhydrol or ordinary
chlorhydrol results in a substantial improvement of the
interlayered product. ~3.8 ml. of diluted (0.5 M in
A12O3~ refluxed (48 hours~ chlorhydrol was diluted
further to 500 ml. 1.26 gms. of Na2SiO3 solution
(containing 28.5% SiO2 and 8.0% Na2O~ diluted to 100 ml.
was added to the refluxed chlorhydrol solution. 12.5
10 gms dry basis #325 Bentonite was added, the slurry boiled
1 hour, filtered, washed 2X with 1/2 1. hot deionized
water and oven dried.
Silicating ordinary chlorhydrol also substantially
improves the hydrothermal stability of the interlayered
clay. 8.5 gms. chlorhydrol was diluted to 900 ml. and
then 1.26 gms. of Na2SiO3 solution (28.5% SiO2, 8.0%
Na2O~ diluted to 100 ml. was added to the dilute
chlorhydrol solution. After aging overnight at room
; temperature, 12.5 gms. dry basis #325 Bentonite was
i::
added, hot aged 1 hour at 150F, filtered, washed 2X
with 1/2 1. hot deionized water and oven dried.
Summarized below is a comparison of the hydrothermal
sta~ility of both of the a~ove interlayered clays with
~ ordinary chlorhydrol interlayered clay.
- Surface Area
Interlayering Species 1-100F6-1400~F, 1 Atm.
Chlorhydrol 270 20
Chlorhydrol + SiO3 2 294 129
Refluxed diluted 2
chlorhydrol + SiO3 353 165
,.
- 27 -
.,
'` ~
346
Example 22
~'
This example ïllustrates the use of the pillared
; interlayered clays -as sorbents :Eor organic molecules.
202 gms. of a ~ 2.0~ slurry of Volclay~ 200 (American
- Colloid Co.~ which corresponds to 4.25 gms. (Dry Basis)
clay was added to 400 ml. of solution containing 7.6 gms.
of aluminum chlorhydroxide solution (Reheis Chemical Co.).
The slurry was aged 1 hour with agitation, centrifuged,
reslurried in deionized water and recentrifuged. The
product was then reslurried in a second solution of
7.6 gms. aluminum chlorhydroxide diluted to l.O 1. After
aging for l hour the slurry was centrifuged, reslurried
in deionized water, recentrifuged and oven dried overnight
at 250F. The sample was then ground and tested for
n-butane and iso-butane capacity after several batches
.. ~
- were prepared. This sample had an n-butane capacity
; of 7.74~ and an iso-butane capacity of 7.13~. The surface
area of this sample was 393 m /gm. and the basal spacing
O
was 17.7A.
~- 20 Example 23
i
This example shows the usefulness of pillared inter-
layered clays as hydrocracking catalyst base. 2,720 gms. of
chlorhydrol was diluted to 6 gallons and 5,000 gms. dry
basis #325 Bentonite was added with vigorous agitation.
~; The slurry was hot aged 1/2 hour at 150F, filtered and
,.,.~
~` washed lX on the filter with 6 gallons of hot water.
.j
The filter cake was reslurried to 15.9~ solids and spray
drïed. The product surface area was 316 m2/gm. and the
;~ O
basal spacing was 18.OA. A portion of this material
:
~ !
~ - 28 -
,.~
:.
i ' ' '
,'`: . . , : ''
,
346
was exchanged with 0.5~ Pd, hlended at a ratio of 9 parts
interlayered clay/1 part A12O3, reduced ~2 hours at
500F, 12 hours at 700F in 71 :Liters/hour flowiny H2~
and then calcined 3 hours at 1000F. The hydrocracking
test was run at 1 LHSV, 15aQ psig and 8000 SCF/B H2.
The interlayered clay hydrocracking catalyst gave 16%
conversion at 675F, compared to 6% conversion for a
0.5 W% Pd impregnated 28% A12O3, 72% SiO2 catalyst.
Example 24
This example shows the general use~ulness of
interlayered clays ~or water sorption. The same
interlayered clay sample ~without Pd) as described in
- example 24 was used ~or the water sorption measurements.
The sample was calcined 1 hour at 1000F prior to the
test. The results, yiven as % water sorption with
varying relative humidity (RH), indicate substantial
` -ability to sorb ~ater.
TV @1750F 4.85
- Ads. 10% RH 2.56
Ads. 20% RH 4.78
Ads. 35% RH 9.30
Ads. 60% RH 12.48
; Ads. 100% RH 19.76
The capacity as a dehydrating agent is comparable to silica
gels and zeol:Ltes.
- 2~ -
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