Note: Descriptions are shown in the official language in which they were submitted.
SYNTH~TIC CRYSTALLINE 5ROU~ VII:t
MET AL SILICATE COMPOSITIONS AND
PREPARATION TH~REO~
The present invention relates to new crystalline
- silicate compositions, particularly Group VIII metal
silicate compositions. ~urther, this invention relates
to methods for producing these new crystalline silicate
compositions and to a method for activating them to
enhance their usefulness for certain catalytic conversion
processes.
Zeolitic materials, both natural and synthetic,
are known to have catalytic capabi,lity for various types
of reactions, especially hydrocarbon conversions. The
well-known crystalline aluminosilicate z~olites are
commonly referred to as "molecular sieves" and are char-
acterized by their highly ordered crystalline structure
and uniformly dimensioned pores, and are distinguishable
from each other on the basis of composition, crystal
20structure, adsorption properties and the like. The
term "~olecular sieves" is derived from the ability
of the zeoli1te materials to selectively adsorb molecules
on the basis of their size and form.
The processes for producing such crystalline
5synthetic zeolites are well known in the art. A family
of crystalline aluminosilicate zeolites, designated ZSM-5,
is disclosed in U.S. Patent No. 3,702,886,
3o
,
, , , , - . ,
92
1 The famil~r of
ZS~i-5 compositions has a ch~ract~ristic ~-ray dl4fraction
pa.tern an, can also be identified, in terms of mole
ratios of oxides, as follows:
7 0.9+0.2 r 52/n ~l2 3 2 2
~herein M is 2 cation, n is the valence of said cation, ~1
is selected from the ~roup consisting of aluminum anc
gallium, Y is selected from the group consisting of silicon
and ~ermanium, and ~ is from Q to 40~ In a preferred synthesized
10 form, the zeolite has a formula, in terms o mole ratios
of oxides, as follows.
- 2/no Al2o3:5-loosio2:zH2o
and M is selected from the group con~istins of a mixture
of alkali metal cations, especially sodium, and tetraal]~
15 ammonium cations, the alkyl groups Cf which preferably
contain 2-5 carbon a~oms.
U. S~ Patent No. 3,941,871 relates to novel crystalline
metal organosilicates wh:ich are essentially free of ~roup
IIIA metals, i.e., aluminum and/or gallium.
It is noted therein that
the amount of alumina present in the known zeolites appears
directly relate~ to the acidity characteristics of the
resultant product and that a low alumina content has been
recognized as being advzntageous in attaining a low degree
25Of acidity which in many catalytic reactions is ~ranslated
into lo~ coke making properties and low aging r~tes. A
typical procedure for making the organosilicates is to
react a mixture containing a tetraa~];ylamr.Gnium compound,
sodium hydro~ide, ar oxide of a metal other than a me~al o~
30Group III~, an oxide of silicon, and water until crystals
of said metal organosilicates are forme~. It is ~lso note~
in the patent that the family of crystalline metal or~ano-
,~
--3--
1 silicates have a definite X-ray di fraction pattern which
is similar ~o tha~ fox the ZS~vl-5 zeolites. ~inor amounts c
alumina are contemplat~d in the p~tent and are attributable
primarily to the presence of aluminum impuritie~ ir, the
5 reactants znd/or e~uipment employed.
U. S. Patent No. 3,844,835 discloses crystalline
silica compositions. The crystalline silica materlals may
also contain a metal promoter which may be selected from
Group IIIA, Group VB or Group VIB e~lements.
U. SO Patent No~ 4,088,605 is directed to the
synthesis of a æeolite, such as ZSM-5, which contains an
outer shell free from aluminum. The paten~ states at
column 10, line 20 et seq., that to produce the outer
aluminum-free shell it: is also essential that the reactive
15 aluminum be removed rom the reaction mixture. It is there-
fore necessary, as not:ed therein, to process the zeolite
and to replace ~hecrystallization medium with an aluminum-
free mixture to obtaincrystallization of SiO2 on the surface
of the zeolite which can be accomplished by a total replace-
20 ment of the reaction mixture or by compleY.ing from the originalreaction mixture any remaining aluminum ion with reagents
such as gluconic acid or ethylenediaminetetraacetic acid
(EDT~).
Crystalline borosilicate compositiOns are
25disclosed in German Offenlegungschrift 27 46 790. This
application relates specifically to borosilicates which are
prepared usin~ the usual procedures for making the alumino-
silicate zeolites. It is noted therein that in instances
where a deliberate effort is made to elirl~inate aluminum
3Ofrom the borosilicate crystal structure because of its
adverse influence on particular conversion processes, the
molar ratios of SiO2/A12O~ can easily eYceed 200n 3000 and
--4--
- that this ratio is generally only limited by the avail-
ability of aluminum-~ree raw materials.
German Offenlegungschrift 28 48 849 relates
to crystalline aluminosilicates of the ~SM-5 zeolite
' sexies. These particular zeolites have a silica to
alumina mole ratio greater than 20 and are prepared
from a reaction mixture containing a source of silica,
alumina, a quaternary al]cyl ammonium compounds and
a metal compound including such Group VIII metals
lO as ruthenium, palladium and platinum. In Example
2, the crystalline aluminosilicate is prepared ~rom
a reaction mixture containing RuC13 and in Example 3,
the reaction mixture contains H2PtC16.nH2O.
While the a:rt has provided zeolitic cata-
15 lysts having a wide variety of ca-talytic and adsorp-
tive properties, the need still exists for crystalline
materials having different and/or enhanced catalytic
properties. For example, an important use for a
crystalline material :Ls in conversion processes of
o~ygenated compounds such as the conversion of dimethyl
ether and methanol to aliphatic compounds as well as
the conversion of synthesis gas or hydrocarbons,
such as ethylene, at a significant level of conver-
sion and selectivity.
3o
The present inventioll rela-tes to crystalline
Group VIII metal silicates which can be identified
in terms of the moles of its oxides in Formula A as
follows:
-
R20: w M20: X B203:ySiO2:z H20n m
where R is tetraalkyl ammonium, hydrogen, alkali metal,
lOmetal ammonium or mixtures thereof, n i5 the valence of R,
M is a Group VIII metal or mixtures thereof,
m is the valence of the Group VIII metal,
v is l0.01-80),
w is (0.01-30),
1~ x is (0 - 40l,
y is 100, and
z is (0 - 200),
with the proviso that when
M is Fe, x = 0 and
20that Al content is less than 100 wppm. The crys-talline
Group VIII metal silicates of this invention have an
X-ray diffraction pattern substantially that of ZSM-5
zeolite.
- The crystalline Group VIII metal silicate which is
25the subje.ct of this invention may be prepared by a method
3o
., "
-6 ~ 2
which comprises: preparing a mixture containing a salt of
a Group VIII metal, a tetraalkyl ammonium compound, alkali
metal hydroxide, silica and water~ said mixture having an
aluminum content of less than about 100 wppm, based on silica,
and having a composition in terms of mole ratios of oxides,
falling within the followi.ng ranges:
OH /SiO2 0.05 - 3
Q /~Q + A ) 0.01
H20/0H 10 - 800
SiO2/M2/mo 3 - 10,000
where Q is quaternary ammonium ion, A+ is alkali metal ion,
M is a Group VIII metal and m is the valence of the Group
VIII metal, maintaining the mixture at a temperature of about
50 to about 250C until crystals of said silicate are formed
and separating and recovering said crystals.
Oxygenated hydrocarbons, such as methanol, dimethyl
ether and mixtures thereof may be converted to hydrocarbons
by contacting said oxygenated hydrocarbons, under conversion
conditions with the crystalline metal silicate composition of
this invention. In a similar fashion, synthesis gas
comprising hydrogen and carbon monoxide, may be converted
to hydrocarbon and/or oxygenated compounds by contac-ting said
synthesis gas, under conversion condi.tions with the crystalline
metal silica-te compositi.on of this invention. Some oE the
compositions of this invention promote the po]Lymerization of
ethylene providing heavier hydrocarbons including aromatics.
The presen-t invention relates to a class of crys-tal-
line Group VIIX metal silicate compositions. These crystalline
compositions axe preparecL by a process which requires that a
' ''~1
.
~2~
-7-
source of a Group VIII metal be present in the reaction mix-
ture, that a chelating agent may optionally be present and that
the amount of aluminum in the reaction mixture be carefully
con-trolled.
In accordance with the present invention there are
provided crystalline Group VIII me-tal silicates which are sub-
stantially free of aluminum i.e., containing less than about
100 wppm (weight parts per million) and which can be iden-tified
in texms of the mole ratios of oxides as set forth in Formula
A aboveO In its preferred form, the Group VIII metal is iron,
ru-thenium, rhodium, palladium or platinum. The silicate, as
prepared, also contains a tetraalkylammonium cation and,
optionally, boron.
Members of this family of Group VIII sillcates
possess a definite crvstalline structure. The x-ray
diffract:Lon pattern of the dried crystalline material of
this invention is substantially the same as ZSM-5 zeolite.
Although the X-ray diffraction pattern does not distinguish
the Group VIII metal silicates of this invention from a
ZSM-5 zeolite there are several major points of distlnction.
SZM-5 zeolites contain substantial amounts of aluminum, but
essentially no Group VIII metals in their crystalline
structure. The silicates of this invention contain substantially
no aluminum, but significant quantities of Group VIII metals
in theiur crystalline structure which cannot be removed by con-
ventional ion exchange techniques. The Group VIII silica-tes
are distinguishable from ZSM-5 zeolite in other respects. In
particular the cataly-tic activity oE the Group VIII silicates
of ~his invention is substan-tially dis-tinct from that of a SZM-5
3() type zeolite.
. . .
,,"~ I
:` ~
-8~
The Group VIII metal silicates of this invention can
be prepared by heating a reaction mixture comprising tetraalkyl
(i.e. tetrapropyl) ammoniurn ion, e.g. from the bromide or
hydroxide, alkali metal, i.e. sodium, hydroxide, a Group VIII
metal compound, an oxide oi silicaon, and wa-ter, usually having
the composition in terms of mole ratios falling within the
following ranges:
~road Preferred
OH /Sio2 0.05 - 3 0.2 - 0.9
10 Q /(Q + A ) 0.01 - 1 0.03 - 0.9
H2O/OH 10 - 800 20 - 500
SiO2/M2O 3 - 10,000 10 - 4000
m
where Q+ is qua-ternary ammonium ion, A is alkali metal ion,
M is a Group VIII metal and m is the valence of the ~roup VIII
metal, and maintaining the mixture at elevated -temperature for
a time sufficient to form crystals of the product.
Typical reaction conditionc; consist of heating the reaction
mixture at elevated temperature, e.g. 50 to about 250C.,
and even higher, for a period of time of ~rom about 6 hours
to as much as 60 days. The preferred temperature is from
about 100 to 190C. for time periods of from 1 -to about
16 days. The reaction mixture can be heated at elevated
pressure as in an autoclave, or at normal pressure, e.g. as
by refluxing. The preferred method of heating the reaction
mixture is at reflux temperature.
As is common practice in the production of sili-
catc compositions, when reflux heating of the reaction mixture
3n
'~f~';
B9~
g
is employed large amoun-ts of sodium chloride along with
some sulfuric acid, are added to the reaction mixture
to ensure crystallization of the pxoduct. Thus, in
reflux preparation, the ra-tios of SiO2/M2O, OH /siO2,
m
and like ratios tend to result in values different from
the ratios of the autoclave processing.
Of course, in the preparation of the reaction
mixture for the heating step, the reaction mixture is
maintained substantially free of aluminum, i.e. contains
less than 100 wppm (weight parts per million), based on silica.
There are various optional embodiments which
can be practiced to obtain compositions having particularly
desirable or enhanced properties. Among the Group VIII
metals, those which are preferred in preparing the metal
silicate compositions of this invention are iron, ruthenium,
rhodium, palladium and platinum. Further, it has been found
that a chelating agent may optionally be employed with the
Group VIII metals where desired. Boron may also be
utilized in preparing the Group VIII metal silicates of
this inven-tion and is preferred for most of the Group VIII
metals. However, the combination of boron with iron is
not within the concept of the present invention. The
combination of boron with chelating agent has proven
very useful for some of these Group VIII metal silicates.
Often, the particular combination of components to be
incorpora-ted in the reaction mixture will depend on the
partic~llar catalytic use for which the silicate composition
will be employed.
3()
/ ~
,, ~!..
-lo~ 32
. .
When a source of boron and/or a chelating agent
is additionally provided in the reaction mixture, the
composition has the following additional mole ratios falling
within the following ranges:
Broad Preferred
SiO2/~2O3 2 - 1000 12 - 500
SiO2/chelating agent 1 - 5000 20 - 1000
The digestion of the gel particles is carried
out until crystals form. The solid product is separated
from the reaction medium, as by cooling the whole to room
temperature, filtering, and water washing.
The foregoing product is dried, e.g., at llO~C
for from about 8 to 24 hou:rs or longer. Of course, milder
conditions may be employed if desired, e.g., room temperature
under vacuum.
An important feature of the invention is a process
for activating the novel crystalline composition of the
invention for enhanced use in various conversion processes.
In general, the activation procedure comprises:
(a) Heat treating the dried silicate composition
at e.g., about 200 to about 900C., preferably
about 400 to about 600C. for about 1 to about 60
3~
. ' ~
8~3~
1 hours, prererabl~ about 10 to about 20 hours in a
molecular oxygen containing atmosphere.
In a preferred embodiment, the activation
procedure comprises:
(1) Heat treating the dried silicate composition
at e.g., about 200 to about 900C., preferably
about 400 to about 600C. for about 1 to about 60
hours, preferably about 10 to about 2C hours;
~2) Ion exchanginy the heat treated silicate
composition with a material which upon further
heat treating decomposes to provide a composition
having a hycLrogen cation;
~3) Washing and drying the exchanged silicate
composition,
(4~ Heat treating the dried silicate using the
procedure of step (l);
It will be appreciated by thos~ ~killed in the
art that steps ~ 4), i.nclusive of the preferred
embodiment, and step ~a), above, are well-known and represent
20 methods commonly used to activate zeolite type catalysts.
The composition of the invention may be suitably employed
in the form obtained after step 4 or after step a. Heat
treating may be done in any atmosphere as is known in the
art and is preferably done in air.
Where desired, the activation procedure may,
optionally, include the Redox Treatment dislcosed in
Belgium Patent No. 886,090. This treatment includes a
heat treatment conducted with a reducing agent and is
practiced, following step ta) or step t4) of the above
3O activation procedures, as follows:
.
-12--
(b) or (5) Treating the heated silicate composition
with a reducing agent for about 1 to about 80 hours,
preferably about 2 to about 40 hours, at about 200
to about gO~C, preferably about 400 to about 600C.,
and
(c) or (6) Heat treating the reduced silicate
using the procedure of step (a) or (1), respec-tively.
Any reducing agent may be used or a compound
which under the treatment conditions forms a reducing agent,
such as dimethylether. Dimethylether and hydrogen are
preferred because of their demonstrated effectiveness.
The activation procedure disclosed herein which does
not include the "Redox Treatment" provides a catalytically
active composition which exhibits useful levels of conversion
and selectivity in the reactions catalyzed by the compositions
of this invention and is the preferred activation procedure.
Although the inclusion of the "Redox Treatment" is not neces-
sary to provide a useful catalyst, subjecting -the compositions
of this invention to Redox Treatment following
oxidative activation may provide some alteration in the
selectivity, usually minor in nature. Therefore, where
economically justified or where slight alteration in
selectivity is required, Redox Treatment may be utilized.
As noted hereinabove, and as known in the art,
the procedure for preparing zeolites, e.g., aluminosilicates,
is well-known. It is an essential feature of the present
invention, however, that the crystalline silicate composition
be prepared using a reaction mixture containing, based on
weight percent silica, less than abou-t 100 wppm aluminum
ions, preferably less than about 50 wppm and a source of a
Group VIII metal cation~ Aside from other differences with
~ ~ -13- ~3~
~.
prior art crystalline silica composition, the silicate
compositions formed herein are substantially free of aluminum
with the molar ratio of SiO~/A~2O3 bein~ greater than about
8,000 and even 3~,000.
It is not known why the crystalline compositions
of this invention provide such unexpected properties as
selectivities with dimethyl ether, ethylene polymerization
and synthesis gas conversion distinctly different from that
obtained with ZSM-5 zeolite. It is possible to theorize
that the Group VIII metals form part of the three dimensional
crystal network and in some fashion not yet understood provide
catalytic properties not evidenced by ZSM-5 zeolites.
Ion-exchange of these same metals into a crystalline
silicate does not provide the same catalytic activity thereby
providing some support Eor the theory that the Group VIII
metal cations form part of the crystalline structure of
the presen-t compositions and in such positions influence the
catalytic properties of these crystalline silicates.
In preparing the crystalline compositions of the
invention it is important that substantially aluminum-free
raw materials be employed. The substantially aluminum-free
silica source can be any of those commonly considered for use
in synthesizing zeolites such as powdered solid silica, silicic
acid, colloidal silica or dissolved silica. A preferred silica
*
source is Cab-O-Sil, sold by Cabot Co.
The substantially aluminum-free alkali metal hydroxide
material is sodium hydroxide, potassium hydroxide and mixtures
thereof.
The group VIII metal salt employed should be substan-
tially aluminum-free as well as the other components
* Trade Mark
~10
-14~ 2~
1 which are employed in formulating the reaction mixture,
viz. boron compounds, chelating agents and the like. Group
VIII metal salts such as the chloride, the nitrate and the
like, e.g. ruthenium tri or -tetra chloride, ruthenium nitrate,
, ruthenium sulfite acid, etc., may be usefully employed.
The valence of the Group VIII metal salt in the
starting material may influence the catalytic properties
of the final composition despite the valence state of this
metal in the catalytic composition. The reason for this
~- is not known but it has been observed in the case of
ruthenium that when the crysta:Lline ruthenium silicate is
prepared from a Ru+2 salt, the catalytic properties are
substantially improved over a ruthenium silicate prepared
from a Ru 3 salt despite the fact that the activation
procedure in botn instances might place the ruthenium in
the ~3 state in the silicate composition.
The chelating agents which may useful]y be employed
in preparing the composition of this invention may be
ethylenediaminetetraacetic acid, gluconic acid, 8-hydroxy-
quinoline-5-sulfonic acid and the like.
Where a component added to the reaction mixture
does not have an aluminum content below about 100 ppm,
its aluminum content must be such that the addition of this
particular component will not result in a crystalline
product with an aluminum content above 100 ppm. Therefore,
to this limited extent, a component may have an aluminum
content above 100 ppm but the component must be employed
under carefully monitored conditions.
The specific crystalline compositions described,
3 when evaluated for catalytic properties without having been
calcined, are inactive possibly because the intracrystalline
free space is occupied by organic cations from the forming
-15-
3~
1 solution. They may, however, be activate~ by heat treatment
using known technlques such as heating in an inert atmosphere
or air at about 200 to about 900C., for 1 to 60 hours. This
mav be followed by ion exchange with am~onium salts and further
~ neat treatment at about 200C to about 900C. if desired.
The crystalline composltion can be used either
in the alkaii metal form, e.g., the sodium form, the
ammonium form, the hydrogen ~orm, or other univalent or
multivalent cationic form. Preferably, either the ammonium
or hydrogen form is employed. They can also be used in
intimate combination with hydrogenating components such
as tungsten, vanadium, copper, molybdenum, rhenium, iron,
nickel, cobalt, chromium, manganese, or a noble metal
such as platinum or palladium where a hydrogenation-
dehydrogenation functic~n is to be performed. Such compo-
ner.t can be e~changed into the composition, impregnated
therein or physically intimately admixed therewith. Such
component can be impregnated in or on to the present
catalyst such as, for example, in the case of platinum,
by treating the crystalline composition with a platinum
metal-containing ion. Thus, suitable platinum compounds
include chloroplatinic acid, platinous chloride and
various compounds containing the platinum amine complexes.
The catalyst, when employed either as an adsorbent
or as a catalyst in one of the aforementioned processes,
ma-i be heat treated as described hereinabove.
3
392
-16-
Members of the p:resent family of crystalline
compositions can have the original cations associated
therewith replaced by a wide variety of other cations
according to techniques well-known in the ar-t. Typical
replacing cations would include hydrogen, ammonium and
metal cations including mixtures of the same. Of the
replacing metallic cations, particular preference is given
to cations of metals such as rare earth metals, manganese
and calcium as well as metals of Group II of the Periodic
Table, e.g., zinc and Group VIII of the Periodic Table,
e.g., nickel. These replacing cations are included within
the definition of R in the formula employed herein to describe
the composition of this invention.
Typical ion exchange techniques include contact-
ing the members of the family of borosilicates with a
salt solution of the desired replacing cation or cations.
Although a wide variety of salts can be employed, particu-
lar preference is given to chlorides, nitrates and sulfates.
Representative ion exchange techniques are dis-
closed in a wide variety oi patents including U.S. Pat.Nos. 3,140,249, 3,140,251 and 3,140,253.
Fol owing contact: with the salt solution of
the desired replacing cation, the crystalline compositions
are then preferably washed with water and dried at a
temperature ranging from 65C. to about 315C. and there-
after heat treated as previously described.
Regardless of the cations replacing the sodium
in the synthesized form of the catalyst, the spatial
arrangement of the atoms which form the basic crystal
lattices in any given composition of this invention
remain essentially unchanged by the described replacement
of sodium or other alkali metal as determined by taking
an X-ray powder diffractionpa-ttern of the ion-exchanged
~0
~, ~
` -17- t~8~3~
l material. For example, the ~-ray dif~r2ction pattern of
several ion-exchanged compositiOns reveal a pattern sub-
stantially the same as that for ZSM-S zeolite.
The compos~tions prepared b~r the instan. inven-
tion are formed in a ~ide variety of particular sizes.Generally speaking, the particles can be in the form of
a powder, G granule, or a molded product, such as extrudate
having a particle size sufficient to pass through a 2
mesh ~Tyler) screen and be retained on a 100 mesh (Tyler~
screen. In cases whexe the cetalyst is molded, such as
by extrusion, the compositon can be extxuded before
drying or dried or pa:rtially dried and then extruded.
In the case of many catalysts, lt is desired to
incorporate the composition of this invention with another
15 material resistant to the temperatures and other conditions
r employed in org~nic conversion processes. Such materials
include active and inactive materials and synthetic or
naturally occurring crystalline compositions as well as
inorganic materials such as clays, silica and/or metal
oxides. The latter m!y be either naturally occurring or
in the form of gelatinous precipitates or gels including
mixtures of silica and metal oxides. Use of G material
in conjunction with the present catGlyst tends to improve
the conversion and/or selectivity of the catalyst in
ce~tain organic conversion processes. Inactive materials
suitably serve as diluents to control the amount of conver-
sion in a given process so that products can be obtained
economically and in orderly manner without employin~ other
means for controlling the rate of reaction. Normally,
3 zeolite materials have been incorporated into naturally
occurring clays, e.g., bentonite and kaolin, to impro~e
the crush strength of the catalyst under commercia~ operati~g
- l a ~ ;28~2
l conditions. These mat:erials, i.e., c12y ~ oxides, etc.
function as binders for the catal~st. It is desirahle
to provide a catalyst having good crush strength, because
in a chemical process the catalyst is often subjected to
handling or use which tends to break the catalyst down
into powder~like materials which cause problems in
processinq. These cla~ binders have been employed for the
purpose of improving the crush strength of the catalyst.
In addition to the foregoing materials, the
catalyst can be composited wi1:h a porous matrix material
such as silica-alumina, silica-magnesla, silica-æi.rconia,
silica-thoria, silica-keryllia, silica-titania as well
as ternary compositions such as s.ilica-alumina-thoria,
silica-alumina-zirconia, silica-alumina-magnesia and
silica-magnesia-zirconia. The matrix can ~e in the form
of a cogel.
~ he following examples are presented as specific
embodiments of the present invention and show some of the
unique characteristics of the claimed crystalline composi-
ti.ons and are not to be considered as constitutin alimitation on the present invention.
~,C
1 ~X~IPLE I
A number of Group VIII silica~es were prepared,
not all are in accordance with the present invention.
r The general procedure for preparing Group VIII sili -
cates and borosilicates will be illustrated for ruthenium
borosilicate catal~st X. A sodium silicate solution (A) con-
taining less than 100 ppm aluminum (based on silica) was pre-
pared by dissolving 80.0 g of high purity silica (Cab-O-Sil)
lO in a boiling solution of 700 ml water and 55 g of a 50-52%
aqueous NaOH solution. A second solution (B) containing 85 g
NaCl, 33 g tetrapropylammonium bromide (TPA-~r), 8.9 g boric
acid, lg g concentrated sulfuric acid, and 400 ml water was
prepared. With both solutions at room temperature, solution
15 s was slowly added to the sodium silicate with stirring. When
the addition was complete, the pH was 9.2, which was adjusted
to 8.5 with sulfuric acid.
A third solution (C) containing 2.0 g of hexamine-
ruthenium (III) chloride in 30 ml of water was added to the
20 above stirred silicate mixtllre. The entire mixture was placed
in a 2000 ml polypropylene flask which was partially immersed
in a hot oil bath at 120C. A reflux condenser was attached
to the flask. After 13 days the flask was removed from the
oil bath and cooled. The solid was washed several times by
25 decantation, collected on a filter, washed with deionized
water and dried at 115C, yielding 82.2 g of final product.
The dried material was submitted for X-ray analysis and had
the same pattern as that published for ZS~1-5 type alumino-
silicate (zeolite). The ruthenium content of -the dried sample
3 was 0.64c-~.
A portion (33.8 g) of the dried sample was calcined
at 538C (1000F) for 22 hours during which it lost 11.5~ of
its initial weight. The calcined material was mixed with a
.
.~ ' - ' ..
-20~ 3~
1 solution of 60 g NH4Cl in 300 ml water and refluxed for 16
hours. After washing, the e~change was repeated a second time
for four hours. The material was filtered, washed and dried,
yielding 28.9 g of ammonium ion exchanged solid with a ruth-
enium content of 0.~8%. Normally before testing, the ammon-
ium ion form is converted to the H-ion form by heating in
air at 538C.
Other preparations of Group VIII metal silicates
were prepared by the same general method just describedr
except that in some cases boric acid was omitted from solution
B. The amount of water used in solutions A and B varied
somewhat between samples. The preparation of the remaining
Group VIII metal silicates is described by listing in tabular
form the nature of solution C (which contains the metal),
whether or not boric acid was used, and pertinent analytical
data. It is understood that the actual synthesis followed
the general method just described. All samples had the X-ray
pattern of ~S~-5.
The details of these preparations which included the
following Group VIII metals, ruthenium, iron, palladium,
platinum and rhodium are presented in Tables II - VI.
The catalyst numbers listed in these tables provide
the correlation between the basic preparation o~ the catalyst
and test runs. The actual ionic form of the catalyst used in
catalytic tests is given with the activity data of
Example II.
3o
:
~n ~ ~ o ~ O ! n ~J
TABLE II
RUTHENIUM SILICATES
VIII,XI,XII,XIII,
Catal~st No. XIV,XVI,XVII IX,XV . - X I,II,III,V,VII
Boric Acid Yes Yes Yes No
Growth Time (Days) 11 ` 14 13 12
Sclu-ion C P~u - EDTA Complex 25 mlsRu Sulfite 2.0 g Hexamine 25 mls Ru Sulfite
(Metal) 1.5 g in 20 ml H2O Acid(21 Ruthenium (III) Acld
40 g Rufl Chloride 3C ml
H20
Analysis
Befcre Ion - Ex
- ~u 0.94% 0.64~ 1.22~
- Al 19 ppm 20 ppm
- B 0.34%
After Ion - E~
- Ru 0.52% 0.92% 0.88%
- Al 80 ppm 20 ppm
- B 0.25% 0.27%
Comments
Q~
~1~ EDTA = ethylene ~;~min~tetraacetic acid
(2) Supplied by PrototechCo., NewtQn Hia,hlands, Mass.
)
w
o ~1 0
Table II - continued
~Ul'r~ U~l SILICATES
Catalyst NTo, IV,Vq XXXVII
Boric Ac~a No No
Gr~th ~ime (~ays) 15 16
Solut_on C 2.884 g lIex- 1.465 g RuC13.xH20
Me-tal) amine Ruthenium 120 ml H20
~III) ~hl~r
44 ml H 0
~nal~-sis
Before Ion - Ex
- Ru 0.56 % 0.41%
- Al 6 ppm 45 pp~
Aiter Ion - Ex
- Ru 0.59~ 0.57%
- Al 44 ppm C~
a~
- - ~ w r~ r~ ~ ~
~n o .n o ul o ~p l J
- TABLE III
P~nthenium - Iron Silicate
Catalyst No. XX, XXI
Boric Aci~ ~ NO
Growth Time 15
Solution r 14 mls ruthenium sulfite
acid 10 mls water
T~. O g FeC13 6=~20
1. 4 5 50s NaOH
100 mls T~7ater t 7
Analysis
Pefore Ion Exchange
Ru Q.52%
Al 20 ppm
FT^. 1 . 4g6
- .~
J
~ABLE IV
Iron Silicates
(Prior Art)a (Prior Art)
Catalyst No. XXXI r XXXIV XXXII XXXIII, XXXV
Boric A~id No No No
Growth Time (days) 15 15 15
Solution C g 3 2 g 13 2 g 3 2
tMetal) 8.5 g 50~ NaOH 3.5 g 50% NaOH 8.5 g 50% NaOH
13.0 g 8 HOS 300 ml H20 300 ml H20 r~
300 ml H20 ~p~
Analysis ~ 3
Before Ion Exchange
~- Fe 1.3% 1.2% 1.3%
Al - 20 ppm 25 ppm
After Ion Exchange
Fe - 1.5%
Al
Comments a. Similar to catalyst of German Offenlegungschrift 27 55 770 tBritish patent
1,555,928~ using Cab-0-Sil Silica.
b. 8HOS = 8-Hydroxyquinoline-5-
sulfonic acid
) ~ y 1--
o ~ n c
TABLE V;
Rhodium Silicates
Catalyst No.XXIII,XXIV,XXV,XXVI XXI:t
Boric Acid Yes Yes Yes No
~ro~-th Til~e (days) 15 16 14
Solution C P~h pentamine chloride Rh - EDTA complex 15 g Rh sulfite acid 0.995 g chle~
(ITetal) in methanol solution 33.3 g Rh/i pentamirs
Rhodium (7II1
Analysis
~ Before Ion Exchange
- Rh 0.58% 0.03~ 451 ppm .
Al 9 ppm 13 ppm 14 p!:~r
` B 0.38% 0.41
After Ion Exchange
Rh 0.71% 0.02% 0,33O,
- Al - 7 ppm 17 ~rlr.
B 0.21~ Q 24%
Comments: very llttle Rh very 7ittle Rh
incorporatedl incorporated,
essentially inactive essentially in- ~
active ~3
w ~`) ~ r~) ~ I~
`JlC \Jl O ~ i~ O `~
TABLE VI
Palladium Borosilicates Platinum Borosilicate
C~tGlyst Mo. XXVIII XXVII XXIX XXX
Boric Acid Yes Yes Yes Yes
Growth Time (days) 15 13 11 11
Solution C Pd-EDTA Complex Pd-EDTA Complex 1.279g K2PtCld 1.3U2 g K Pt~la
etal) g 2 2 2 4.lg 8~Qs~
150 ml water 2.5a 5C~ ~la;~
Analysis ,~
Befcre Ion Excbange Pd = 0.98% Pd = 0.61% Pt = 0.69% Pt = 0.1
Al = 112 ppm Al = 13 ppm Al = 7 ppm Al - 5 prm
~ = 0.46%
Na - = 0 . 58
After Ion Exchange Pd = 1.06% Pd = Q.58% Pt = 0.65% Pt = 0.12~
Al = 16 ppm Al = 13 ppm Al = 11 ~pm
Comments *
8-Hy~ro.~linol~e-5-sulfonic acid
~` A
a~
- -25~ 2~32
~ EXAMPLE II
The silicate compositions prepared in Example I
were evaluated for their catalytic pro~erties in a series
5 of tests emploving such feedstocks as dimethyl ether (DME),
ethylene, methanol and synthesis gas (mixture of C0 and H2).
The following compositions were evaluated:
A. Ruthenium sillcates of Table II
B. Ruthenium borosilicates of Table II
10C. Ruthenium iron silicate of Table III
D. Iron silicates of Table IV
E. Rhodium borosilicates of Table V
F. Palladium borosilicates of Table VI
G. Platinum borosilicates of Table VI
The evaluation results are as follows (the catalyst
designation refers to the catalyst preparation set forth in
the appropriate table of Example I:
-27-
A. SiO2/Ru2O3 Compositions of Table II
1. DME Test Data
The c~talysts were all in the H+ form and were
tested with 1.5 g DME/g.cat./hr. at 6 psig. The choice
-' of the ruthenium salt is critical for activity.
Catalyst II III ~ XXXVIIC
Ru ~orm H[RU(OS02H)20H] H[Ru(OS02H)20H] H[Ru(0S0?H)2OH] Ru(~I3)~C13 RuC13
Te~p. C. 420500 420 500 420 500 420 500 420 500
% HC YieldlC)95 99 95 97 93 95 1 1 6 7
% HC Sel.lC)
; Cl 7 8 ~' 6 1 2 100 100 17 17
C2 0 0 0 1 2 3 0 o 2 0
11 26 17 17 13 13 0 0 12 6
C4 27 25 16 2~ 22 24 0 0 46 75
C5+ 53 38 61 51 58 54 0 0 23 2
Ar. 2 2 4 3 4 3 0 0 0 0
a. Same catalyst preparation as I except different ion
exchange.
b. Prior art catalyst similar to that of German Offenlegung-
schrift 28 48 849 using a ruthenium amine complex.
25 c. Prior art type catalyst prepared with a Ru3+ salt in a
fashion similar to the above German patent application except
that a purer source of silica was used.
These results show the critical dependence of the
ruthenium form introduced into the growth solution on DME
3G activity. The sulfite acid H[Ru(0S02H)2OH] is Ru and the
ammine complex is Ru3+. German Offen. 2,848,849 employs a
Ru salt. These data may not firmly establish an
oxidation state-activity correlation they do indicate
such a relationship may exist. All of the above catalysts
-28-
l contain approximately 20 ppm aluminum, well outside the
broad range reported by the prior art. Catalysts I, II, and
III show the reproducibility of the ion exchanqe and testing
procedure. Catalyst IV, corres~onding to the prior art,
was inactive. Catalyst XXXVII, also a prior art catalyst,
showed significantly less activity and different selectivity
compared to catalysts I, II and III.
2. Ethylene Test Data
Both catalyst:s were tested in the H form with 1.5 g
C2H4/g. cat./hr. at 6 psig and 420C.
Catalys~ I IV XXXVII
Ru FormH[Ru(OS02H)20H] Ru(NH3)6C13 RuC13
15 ~ HC Yield (C) 5 0 0
~ HC Sel. (C)
Cl _ _
C2H6 0 _ _
C4 39
5+ 0
As observed with DME, only the Ru2+ gave an active catalyst
with ethylene.
3. Methanol Test Data
All catalysts were in the H~ form and were tested
25 with 1.5 g CH30H/g.cat./hr. with a N2 cofeed (CH30H/N2~1).
Catalyst I II III~ XXXVII
.. . .. .
Tem~. C 420 420 500 500 500
~/~ HC Yield(C)94 35 67 71 3
~,C ~ HC ~el.~C) 0 0 1 2 65
C~ 0 2 3 3 0
C3 0 37 0 0 0
C4 3 41 13 8 35
C5+ 96 20 82 76
Ar. 1 0 0 11 0
-29-
- a. Same catalyst preparatlon as I except different ion
exchange.
Some discreparLcy in data at 420C, but data at
500C is consistent.
4. Synthesis Gas Test Data
All catalysts were tested in a 310 stainless steel
reactor at 735 psig and a space velocity of about 60 hr 1,
Ions were introduced by exchange technique unless otherwise
lO noted.
: 15
''
3
~_rl O ~ O ~Jl O
S iO2~Ru203
Rua Ion MolarTemp. Yield7. HC Sel. (C) Yield 7~ Oxy Sel. (Cl
CstAlvst Form_ orm H~/CO C(C~ Cl C2 C3 C4 5+ Ar (C) 2 3 O~ber
S.A. H + 2 200 7 78 22 0 0 0 0 0 - - -
350 47 ~8 22 0 0 0 0 19 100 0 0
Y S.A. Li+ Z 350 21 4315 11 1 29 0 13 83 4 11 C2~J50!~
A. Ll 1 270 i 79 21 0 û 0 0 1 100 0 0
370 44 48 17 2 25 8 0 25 100 0 û
- YII S.A. Mg 2 2S0 71 990 0 0 0 0 22 96 3 1 C2H50il
- 300 62 99 1 0 0 0 0 12 100 0 0
350 68 99 - 1 0 0 0 0 18 . 100 0 0 w
a S A e H~Ru~0502~{)20H~, A. ; RU(NH3~6cl3
b. Impregn~ted into the H+ form.
-31~ 2~
1 The test data show that SiO2/Ru2O3 catalysts have
good methanation activity in the H form, and especially when
impregnated with Mg2 , The presence of Li retards methan-
ation and gives higher molecular weight hydrocarbons. At times
oxygenates other than C02 were produced~ These Li effects
occurred regardless of the ruthenium form employed.
; 25
3o
B- Si2/B2Q3~RU23 CmPOCitions of Table II
1. DME Test Data
All catalysts were in the H+ form and were tested with
1.5 q DME/G.cat./hr. at 6 psig.
Catalyst VIII IX X
Ru Form Ru2+-EDTA H~Ru(0S02H)20Hl RU(NH3)6C13
Temp. C 420 500 420 S00 ~20 500
10 ~/O HC Y~eld(C) 73 95 99 99 6 5
% HC Sel.(C~
Cl 0 1 4 3 10 23
C2 0 1 1 3 0 0
C3 21 21 29 22 5~ 19
~4 22 21 13 26 17 50
C5+ 55 55 50 42 21 8
Ar 1 0 3 4 0 0
As observed in A-l above, both Ru2+ forms above
showed high activity while the Ru3+ (X) was relatively in-
20` active. Catalyst IX gave results very similar to the boronfree catalysts in A-l above. Catalyst VIII has no boron
free counterpart, but gives similar results to IX~ Catalyst
X prepared with a Ru+3 souFce shows low activity.
2. Ethylene Test Data
Catalysts VIII, IX, and X were inactive with a feed of
1.5 g. C2H4/g.cat./hr. at 6 psig~
3. Methanol Test Data
Only catalyst X was tested, and it was inactive.
4. Synthesis Gas Test Data
All catalysts were tested in a 310 stainless steel
tubular reac-tor at a space velocity oE about 60 hr. 1.
Ions were introduced by exchange techniques unless other~ise
noted
SYN-GAS
SiO2/B2O3/Ru2 3
% HC
% HC Sel.(C) Yield ~ Oxy.Sel. (C)
Rua Ion Molar Press. Temp. Yield Cl C2 C3 C4 C5+ Ar (C)C-O2 3 Other
Catalysl Form Form H2/CO (psig) C (C)
IX S.A. H 1 500350 3446 7 711 29 O 9 100 0 0
XT EDTA H (HCl) 1500 350 2387 13 0 0 0 0 2 100 0 0
XII EDTA NH4+ 1 500 350 2790 10 0 0 0 0 1 100 0 0
XIII EDTA Li 1 500300 324 6 72 80 0 1 100 0 0
35024 3326 3 038 0 9 50 324 C2H5OH
4 C2H4O
C3 70H
12 C4HgOH w
XIV EDTA 1i 2 735420 5784 16 0 0 0 0 39 100 0 0
`XV S.A. Li 2 735350 267 33 0 0 0 0 1 100 0 0
42045 5842 0 00 0 20 99 01 C2H5OH
XVT EDTA Cs 1 500350 485 15 0 0 0 0 1 86 2 12JC2H5H
~C3H70H
~ C4HgOH
XVII EDTA La3+ 2 735 300 1613 4 0 0 82 0 2 16 42 32 C7H4OH
35065 50 11 02 36 0 16 32 10 8 C2H5OH
a. S.A. = H[Ru(OSO2H)OH], EDTA = ethylenediaminetetracetic acid
b. impregnation of H form.
~ -34- ~ ~2~2
The effect of boron on ruthenium silicates can be
determined by comparison of XV above and V (Section A-4).
Both catalysts were prepared using ruthenium sulfite acid.
At 350C the boron containing catalyst (XV) gave greater
C2 hydrocarbon selectivity, much lower hydrocarbon yields,
and no alcohols when compared to V, the boron free catalyst.
Hydrocarbons C3 and greater, as well as oxygenates
other than CO2, are maximi2ed a-t S00 psig. The Li+ further
enhances oxygenates and the hydrocarbons C3 and higher.
Catalyst XVII with La3 is an exception, since oxygena-tes
and higher hydrocarbons are formed at 735 psig.
-35 1~Z89Z
C- sio2~2o3~Ru2o3 COmPOSitlons of Tabl~ III
l. DME Test Data
A comparison amon~ SiO2~Fe203/Ru203, SiO2/~e203, and
~~ Sl02/Ru203 catalysts are given below. All catalysts were
tested in the H form at 1.5 g DMEjg.cat./hr. and 6 psig.
Catalyst XX "Prior Art"a Ib
5iO2/Fe2o3/RU2o3 SiO2/Fe203SiOz/Ru~0
- /
Tem~. C. 420 500 420 500 420 500
~/0 HC Yield(C)lOO 99 9g(100)99(100)95 99
/0 HC Sel.~C)
CL 2 8 3(7) 5(6) 7 8
C2 3 7 3(0) 8(9) 0 0
C3 9 ~ 17(22~ 16(26) ll 2~
C4 22 30 2~(21) 19(15) 27 25
C5+ 55 19 40(43) 14(21) ~3 38
Ar 8 27 15(7) 38(23~ 2 2
a. Similar to catalyst of German Offenlegungschrift 27 55 770
(e~uiv~ to British 1,555,928).
b. See Section A l abo~e.
c. ( ) Values of a repeat synthesis.
3o
~` -36~ 2~
1 Catalyst X~ contains properties of both the ruth-
enlum catalyst and iron catalyst. Tlle closest similarit~
in terms of DME results is with the iron catalyst. The
primary difference between XX and the iron catalyst is in
C~ selectivity. Since the ruthenium catalyst gave relatively
hig~ C4 selectivity, the ruthenium component of XX may be
responsible.
2. Ethylene Test Data
Comparisons of catalyst XX with SiO2/Fe203 and SiO2/Ru2o3
catalyst are gi~en below for a feed of 1.5 g C2H4/g.cat./hr.
at 6 psig. All catalyst-3 were in the H+ form and were tested
at 420C~ a b
XX "Prior Art" I
Catalystsio2/Fe23/RU23sio2/Fe23Si02/RU203
% HC Yield (C) 17 26 5
% HC Sel. (C)
Cl 2 o o
C2H6 16 7
C3 13 o 5
Ca 37 3 39
C5+ 30 90 55
Ar 1 0
a. See Section C-l above,
b. See Section A-2 above.
3o
-37~ 2~
1 ~ased on ethylene data, catalyst XX is unlike th~
iron or ruthenium silicate catalysts. Catalyst XX has the
increased C4 fraction as does the rutheniurn silicate catalyst,
but also contains significant C3 and C2H6 fractlons, un]ike
r)the ruthenium catalyst. Catalyst XX is unlike the iron
silicate catalyst in hydrocarbon selectivities.
3. Met:hanol l'est Data
A comparison of catalyst XX with SiO2/Fe2O3 an~
Sio2/Ru2O3 catalysts is given below. The feed was 1.5 g.
lO C~OH/g.cat./hr. at 6 psig with a N2 cofeed at molar ratio
CH~OH/N2 of about one. All catalysts were in the H form.
Catalyst XX "Prior Art ~Ype"a Ib
sio2Fe23/RU23 SiO2/Fe2 3 Sio2/Ru2o3
Temp. C 420 500 420 500 420 500
15 ~ HC Yield(C)9~ E2 ~ g9 35 ç7
X.C Sel.~C~
Cl 1 6 1 7 Q
C2 2 6 3 8 2 3
C3 1 23 0 5 37 0
20 C4 14 26 4 42 41 13
C5~ 79 20 88 16 20 ~2
Ar 3 1~ 3 22 Q Q
a. See Section C-l above.
. See Section A-3 above.
O~erall, catalyst ~.~ is very similar to the iron sili-
cate catalyst with the exception that a relativel~ large C3
fraction was formed at 500C with ~X. The ruthenium silicate
catalyst did contain a significant C3 fraction at 420C, but
not at 5Q0~C.
3o 4. Synthesis Gas Test Data
SiO2/Fe,7O3/Ru2O3 catalysts in the ~ and Li form
are shown below. All runs were ~/1 H7/CO at 735 p5iC~, and other
conditions are listed. Comparison to SiO2/~u2O3 catalysts
~ Section A-4 above is difficult, ~ince data were obtained
35 at different H2/CO ratio.
~n o ~ n o ~n o
7. HC Sel. ~C) 7. OH Sel. (C~
Cat~lv~:t Form _23co VeL. (hr~l) CP Yiel~(C) CL C2 C3 C4 C % Oxy~ CO CH C
X.~ H~ 1 56 300 5 6931 0 00 0 1 100 0 - O
-- 60 350 11 6535 00 0 0 10 73 8 3 C21H50H
U2 3 ~ . L6 C31170H
84 350 10 6832 00 0 0 6 100 0 0
XXI LL 1 56 300 3 7327 0 0 0 0 2 87 8 4 C21'5CH
-- 60 350 Z4 4218 3 11 6 0 16 74 2 2 C2H50H
F;u203 2Z 1)`1~:
96 300 3 7624 0 0 2 8~ 9 8 C2H50H
104 350 16 4220 2 9 27 0 9 89 3 3 C2~5(~.1
5 D~
~'
_39_ ~ 28~3~
D. SiO2/F`e~O~ COlTlpOSitiOns of Table IV
l. DMF Test Data
The Gatalysts were tested in the H~ and La~~3
forms with 1.5 g DM~/g.catalyst/hour. The La+3catalyst
5 was prepared according to the ion exchange procedure
described hereinbe~ore.
(Prior Art) (Prior Art)
Catalyst XXXI XXXII XXXIII
Ion Form Ht H H+
Temp. C420 500 420 500 420 500
% HC Yield (C) 100 l00100 l00 99 99
% XC Sel. (C)
Cl 7 7 7 6 3 5
C2 0 6 0 9 3 8
c3 `8 5 22 26 17 16
c4 24 26 21 15 22 19
C~+ 5~ 2~343 21 40 14
l-~ Aromatic 7 213 7 23 15 38
% Aromatic
Sel. (C)
C6 l 2 0 4 3 2
C7 l0 ~` l0 13 - 9 14
C8 45 38 4B 43 48 45
Cg 35 ~i~34 31 32 30
Clo 9 12 9 9 8 9
Catalyst XXXII and XXXIII showed higher C3 and
lower C5+ selectivity than catalyst XXXI.
3C
-40-
~ Catalysts in the La form were evaluated under the
same conditions as above.
(Prior Art)
C~talvst ~XIV
Si2/Fe23 (~HQS)-La Sio2/Fe2o3-La
Temp. C. 420 500 420 500
% HC Yield (C)100 99 100 99
10 % HC Sel. (C)
Cl 6 5 5
C2 0 5 o g
C3 ~o 1~ 12 9
C4 2I 2Q 26 21
C5+ 41 3~ 4~ 31
Aromatic 12 2~ 9 22
% Aromatic
Sel. (C)
C6 1 3 1 3
c7 14 15 12 15
C8 49 42 47 41
Cg 30 30 32 32
C10 6 9 8 9
The La3+ exchange of the prior art catalyst
decreased aromatics and increased C5+ selectivity (compare
catalyst XXXV with XXXIII). Little change was noted with
25 the catalysts of this invention (compare catalyst XXXIV with
catalyst XXXI).
2. Ethylene Test Data
The catalysts were tested in the H form at 6 psig
30 with a feed of 1.5 g C2E[4/g.catalyst/hour,
(Prior Art)(Prior Ar-t)
1 Catalyst XXXI XXXII XXXIII
% HC Yield (C) 23 31 26
E-IC Sel. (C)
Cl 3 0 0
C2H6 14 ~ 6 7
C3 11 3 0
C~ 36 1~ 3
C5+ 20 73 90
Aromatic 17 0 0
10 The iron sili.cate catalyst of the invention XXXI
produced significant qu.antities of aromati.cs while catalysts
XXXII and XXXIII yielded only non-aromatic hydrocarbons,
particularly C5+3+
The La exchanged catalysts were tested under the
15 same conditions as the H catalysts.
(Prior Art)
Catalyst XXXIV XXXV
SiO2/Fe203(8HQS)~LaSiO2~Fe203-La3+
; 20 ~ HC Yield (C) 26 45
% HC Sel. (C)
Cl 1 1
2H6 6 25
c4 62 46
C5+ 26 25
25 Aromatic 2 0
The lanthanum exchange produced a marked increase
in C4 selectivity for both catalysts~
3o
,
2~
-42--
1 3. Methanol Test Data
The catalysts were tested in the H form at 6 psig
with a feed of 1.5 g CH30H/g. catalyst/hour and N2 at a molar
ratio C~l~0}-1/N2 of about one.
(Prior Art)
Catalyst XXXI XXXIII
Temp. C 420 500 4Z0 500
% HC Yield ~C) 92 88 98 99
10 % HC Sel. (C)
Cl 1 9 1 7
C2 3 9 3 8
C3 4 14 0 5
C4 51 17 4 42
C5~ 39 23 88 l22
Aromatic 2 29
% Aromatic
Sel. (C~
C 1 1 5 2
C7 7 7 9 11
C8 41 37 40 41
C 40 42 35 36
C9 11 13 11 1~
CatalystXXXI produced results comparable to those
with DME while catalyst XXXIII gave less aromatics as compared to
DME.
Bothcataly~ts in the La3 form were tested at 6 psig
with a feed of 1.5 g CH30H/g. catalyst/hour and N2 at a molar
ratio CH30H/N2 of about o~e.
3o
2~
-~3-
(Prior Art)
1 Catalvs-t XXXIV XXXV
Si2/Fe23(~HQS)-La SiO2/Fe2O3-La
Temp. C 420 500 420 500
% HC Yield (C) 97 9g - 98
- ~ % HC Sel. (C)
1 ~ 5 - 7
C2 3 8 _ 10
C3 15 _ 19
C4 14 31 23
c5+ 80 25 - 23
10 Aromatic 2 16 - 19
% Aromatic
Sel. (C)
C6 1 2 - 1
C7 6 11 ~ 9
C8 41 39 - -37
15 Cg 38 36 _ 38
C10 14 12 _ 15
La3 did not significantly chanqe the methanol
results of catalyst XXX[II. However, at 500~C catalyst
XXXIV prepared with 8HQS gave more C4 and less aromatics in
20 the La3 form than the H form (see catalyst XXXI).
4. Synth~sis Gas Test Data
Not tested
_ 2-_2O3/Rh2O3 Compositions of Ta~le V
Svnthesis of t:he rhodium-borosilicate is very de-
5 pendent on ;he rhodium form introduced into the growth solution.
With Rh -EDTA or H[RhlOSO2H)2OH], very little rhodium was
incorporated and essentially inactive compositions resulted.
When Rh -ammine complex was used, rhodium was incorporated,
and catalytic activity was present.
3~1
l l. DME l~est Data
The H form clf the catalyst prepared with Rh
ammine complex (XXIII) was tested at 370C, 420C, ~nd 500~C
with l.5 g DME/g.cat./hr. at 6 psig. The only reaction ob-
- ~ served was radical decomposition of DME:
CH30CH3 ~ CH4 + H2CO
H2CO s H2 + CO
This reaction is thermally induced at about 500C over
SiO2/B2o3 catalysts, but with the rhodium composition, nearly
complete decomposition of the DME was observed at temperatures
as low as 370C. No significant hydrocarbons other than CH4
15 were observed~
2. Ethy:lene Test Data
Catalyst XXIII was inactive with C2H4 at 420C.
3. Methanol Test Data
Not Tested.
4. Synthesis Gas Test Data
A SiO2/B203/~1203 catalyst prepared from Rh -ammine
was tested with l/l H2/CO at 500 psig.
Catalyst XXIV XX~
Ion Form NH4+ Li+
Tem~. C 420 350 420
~/0 HC Yield(C) ll 3 45
3 C3 960
C4 0 0 0
Ar o O O
% Oxy.Yield(C~ l 4 45
~2 lOO lOO lOO
C~1301~ 0
Other
3f3;~
--45--
1 The rhodium compositions exhibit methanation
activity, par-ticularly XXV at ~20C.
5. Water Gas Shift
0.50 g. of tlle 5iO2/B203/Rh203 catalyst (prepared
with Rh +-ammine) and :lO.O ml deionized water was charged to
a 70 ml 316 stainless steel reactor. After purging with CO,
the reactor was pressurized with CO to 750 psig. The vessel
was heated and maintained at 150C for two hours with shaking.
1 After two hours the reactor was cooled to ambient temperature,
the gas vented, measured, and analyzed. Co2 yield used to
determine H2 produced.
Catalyst XXIV XXVI
15 Ion Form _ 4 _ Na
mMH2/mMRh/Hr. 2.7 5.6
6. Hydroformylation
The reaction of formaldehyde with synthesis gas to
yield glycolaldehyde was catalyzed by catalyst XXIV. The
reaction was conducted in a 70 ml. Parr bomb with a glass
liner, and was shaken during the reaction period. The re-
; actor was charged with 0.50 g (16.7 mM) formaldehyde, 5 ml of
a mixture oftetraglyme-tributylphosphine oxide (10:1 by wt.),
5 and 1 g. of XXIV (.01 g.Rh). After pressurization with 3500
psig H2/CO (1/1), the reactor was heated to 130C for 30
minutes, and then cooled. After venting the gas mixture,
catalyst was separated by centrifuging, and the liquid analyzed.
Methanol (2.5 mM), glycoladehyde (3.2 mM) and ethylene glycol
~ (0.3 mM) were found. Thus the following turnover numbers were
achieved.
'
'
-46 ~ 2
l 52 moles Cll30H/mole Rh/hour
66 moles HOCH2CHO/mole Rh/hour
6 moles HOCII~CH2OH/mole P~/hour
The catalyst was separated from the product mixture, recharaed
~ with fresh reagents, and tested as before. The turnover numbers
were:
29 moles CH30H/mole Rh/hour
66 moles HOCH2CH0/mole Rh/hour
2 moles HOCH2CH20H/mole Rh/hour
When the catalyst was iLsolated from the second use, N-methyl-2-
pyrrolidone (95%) was substituted for the tetraglyme-tributyl-
phosphine oxide and ret:ested. No glycolaldehyde was produced,
but 52 moles CH30H/mole Rh/hr., and 2 moles HOCH2CH20H/ mole
~5 Rh/hour were found. The catalyst had become dark purple, sug-
gesting the presence of a rhodium cluster.
F. SiO2/B~03/PdO2 Compositions of Table VI
l. DME Test Data
Two catalysts were prepared according to the same
procedure using pd2 -El)TA complex in the catalyst growth
solution. Both catalysts were tested in the H form with 1.5
g DME/G.Pd/hr. at 6 ps:lg.
Catalyst XXVII XXVIII
Temp. C 420500 420 500
% HC Yield (C) ll 4 74 84
% HC Sel. (C)
Cl21 90 2 7
C22 3 3 0
C35 7 25 lO
C 0 0 24 23
c5+ 71 0 46 59
Ar0 0 0
Reproducibi.lity of catalyst was not good.
2, Ethylene Test Data
Both ca-talysts unreactive.
3. Methanol Test Data
Not available.
-~7~ 2
1 4. Synthesis Gas Test Data
~ atalyst XXV:[I was H2 treated at 420C and tested
with H2/CO (1/1), 735 psig, 350C at a space velocity of
about 60 hr
~/O HC Yield~C) a
~/O HC Sel.(C)
Cl 77
C2 23
C4 0
ar
% Oxy.Yield(C) 4
~/O Oxy.Sel.(C)
CH2OH 97
Other 0
G. SiO /B O3/PtO2 Compositions of Tahle VI
Two catalysts were prepared using pt2 -chelate,
20 where in one case the chelate was EDTA, the other was 8-hydroxy-
quinoline-5-sulfoni~ acid (8HQS).
1. DME Test Data
Catalysts were tested in the H form with 1.5 g.
25 DME/g.cat./hr. at 6 psig.
Cata 1YS ~ XXIXa XXIXb X~Xb
Chela~e EDTA EDTA 8HQS
3 Tem~. C 420 500 420 500 420 500
% HC Yield(C) 6 8 14 22 6 11
/~ ~IC Sel.(C~ 2 14 21 49
Cl 4~ 0 0 5 0 0
C 44 34 41 17 42 2~
C~3 4 3 23 13 33 14
CS~ 4 18 35 49 2 13
Ar 0 0 0 2 0 0
a. Catalyst activated at 500C in air
b. Catalyst activated in 540C in air
, ' ' . ,
.
~48~
Catalyst X~IX activated at 500C gave very selective
production of C2, C3 hydrocarbons, which is very important
from a commercial point: of view. The 540C activation temp-
erature eliminated C~, but not C3 hydrocarbons. The 8HOS
5 catalyst similarly gave high C3 production, but CH4 selectivity
was greater.
2. Ethylene Test Data
Both ca-talyst: XXIX and XXX were inactive.
3. Methanol Test Data
1 Catalyst XXIX, air activated at 540C, gave only a
3% yield of C5+ hydrocarbons. Catalyst XXX was not tested.
4. Synthesis Gas Test Data
Catalyst XXIX, which had been activated at 350C, was
15 tested with H2/CO (1/1) at 735 psig and a space velocity of
about 60 hr 1.
Temp. C 250 300 350
/O HC Yield(C~ 1 16 38
29~/O HC Sel.(C) 20 73 54
Ccl2 800 270 223
3 0 0 7
C54~ 0 0 15
Ar
~/O Ox~.Yield(C~ 1 10 32
25~/ oxv.sel.(c? 84 95 94
CO~eOH 2 D~
3o
The results a-t 250C are unusual due to the extremely
high C2 production, even though the yield is very low.
