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Патент USA US2107611

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Patented Feb. 8, 1938
, ‘ UNlTEo-sTiA-TEs Pars-yr
. 5. minim LAN‘D
mz'rnon or rimrsnme' ' '
'rrm SAME
. ‘Carl 11.3. Jarl; mm on. Andaman G. may.
Pleasant Ridge, Mich; assignon ‘to, Beck, Kol» ,
" vler a‘ Company, Inc., Detroit, Mich.
‘No nmvlnr. Application May 29, 1937. '
Serial No. 145.633
' from“. (01. 23-238)
‘This invention‘relates to'improvements in the objections by using binders which are either
preparation of catalysts and particularly such completely
volatile ~without decomposition at or
catalysts asareused in the vapor phase catalytic below_ the operating
temperature, or which. are
depolymerized to form products'which-are‘easily
91 Heretofore much di?lculty has arisen ‘in at
- tempting to secure the catalytically ‘active ma
1 terials to the proper place in theapparatus. A
coated catalyst is the .most common form, the
coating at present being applied by various
methods. One. method isbyevaporating asolu
tion, suspension or colloidal solution vof the cata
volatile without carbonization. 'As an example 5
ofga binder of the ?rst type we can mention'in
general pure alkyd resins which ‘consist of
polyhydricealcohol-polybasicracid condensation
products without further modi?cation; An ex;
ample of the second type is polystyrol resin which i 10'
is made by polymerization of styrol.> This‘de
evaporation of water or-some other solvent to. polymerizes, upon, heating, to a volatile liquid
without carbonization. The: invention- is-not
deposit the catalytic material on the porous ma
limited to these two examples but is intended to
terial. 'After evaporation the irregularity oi‘ sur
lytically active material and depending upon
face‘ of the’carrier isdepended, upont- tokhold
the catalytically reactive materials in place. An
other method consists of spraying .a solution,
suspension or colloidal solution of the catalyti
20 cally reactive material onto the carrier, which
.y y.
Ammonium meta _vanadate___...v _________ __ 245' _
‘Silver nitrate_________ __'__.__j___-_,.._'____:___ 3.5 20
form‘. distribution 1 of material on the surface.
Neitheriof these methods produces a catalyst
Alkyd resin_.'_-_'___"_ ____________ __'_'_ ____ __
that can stand verymuch'mechanical handling
dusting or ?aking voft is‘ considerable. Even if
I this material ‘is‘recovered‘thereis a great loss in
e?iciency during the process due to partially ex
posingthe carrier.
We have tried to overcome the lack of adhesion
by the use of binders. While inorganic binders
such as silicic acid, phosphoric acid, silicate of
soda or potash and the like are capable of giv
ing permanent adhesion, nevertheless, in most
35 cases the use 01’ these binders is very objection
able because they tend to start undesired side re
actions and also tend to form a permanent coat
ing over the catalytically reactive particles, and
thus their value is impaired since they are insu
40 lated from contact with the substance in the
gaseousv phase which is to be catalyzed.
In the case of most of the organic binders we
have found that .upon attempting to remove
them by burning them oil, a very undesirable
is generally kept in. motion so as to insure uni
25 and the loss of. catalytically reactive material by
include all types of resinous binders which vola- l5
tillze completelywithout carbonization.
tendency toward carbonization takes place. The
presence of the finely divided carbonaceous par
ticles gives in e?ect a reduced catalyst which en
tirely' defeats the purpose for which the process
is intended. In the case of vanadium pentoxidel
50 catalyst, which changes to vanadium dioxide and
back and iorth in the oxidation of organic ma
terials, its ef?ciency is greatly impaired it it is
reduced down to lower oxide stages, for instance
the sesqui-oxide.
The present invention entirely overcomes these
The alkyd resin may be made by condensing
in known manner, 200 parts by weight of
phthalic anhydride and 100 parts by weight of 25
glycerine, by heating to 200° C. until the prod
uct has a melting point of 115° C.
' These materials are ground together in a ball,
mill ?rst dry, and are then ground again wet
after addition of 600 parts by weight of acetone. 30
The resulting suspension is sprayed onto 3850
parts of quartz chips, which had previously been
etched in caustic soda and washed with hydro
chloric acid.
The resulting catalyst is air-dried to remove 35
acetone and is then placed in the catalytic con
verter which is slowly heated to about 400° 0.,
while a stream of air is led through it. The
stream of air is employed to sweep oi! the vapors
generated. When the catalyst is treated in this 40
manner the alkyd resin vaporizes oil! completely
leaving no carbonaceous residue. The catalyst
may be used with excellent results for conversion
01' naphthalene to phthalic anhydride.
Example II
240 parts of ammonium vanadate are heated
under agitation to about 375° C. The vanadium
, pentoxide thus obtained is ?nely divided and can
be directly mixed with a vehicle consisting of 50
20% acetone solution of a resin made by con
densation of 1 mol. 0! ethylene glycol and 1 mol.
oi.‘ phthalic anhydride.
The catalyst is sprayed and treated as in the
previous example and may be used for dehydro- 55
genation ‘of “methyl alcohol ‘tovv formaldehyde,
oxidation of naphthalene to :phthalic anhydride
and similar - processes.
Example III
A vehicle consisting of 15 parts of polystyrene
and 100 parts oftoluene ismixed‘with 100 parts
of vanadium pentoxide made‘ by ~decomposition
by ‘heat' ofammonium meta vanadate. Proper
10 consistency for spraying is maintained by addi
used advantageously to decarboxylate phthalic
anhydride to form benzoic acid and carbon
We claim:-_
1. In a process for the preparation of catalysts
by coating a carrier with catalytically active
material and a binderyandthen- volatilizing the
binder; the improvement wherein the binder em
ployed is selected from a group consisting of un
modi?ed polyhydric aicohol-polybasic acid, con 10
tion of toluene and the~mixture is sprayed onto; densation products andv resins formed by the
2000 parts- of quartz.
polymerization of styrol.
This catalyst may be used for many purposes
2. .Theprocesslas set ‘forth in claim 1, wherein
particularly for conversion; of‘ methanol to ‘for- ‘ the binder is an ‘unmodi?ed polyhydric alcohol
maldehyde; and naphthalene .to phthalic "an
polybasic acid‘ condensation product.
‘ 3; The process as set forth in claim 1, wherein
, hydride.
the binder is a reaction product of phthalic an
Example IV a
catalyst for reduction of carbon
monoxide with hydrogen to form formaldehyde
20 is prepared ‘in the following manner:-120 parts
of-manganesecarbonate, 140 parts of ammonium,
meta vanadate, 49r<parts~ of=qsilver nitrate, 30=parts
hydride and glycerine.
4. The process as set forth in claim 1, wherein
the binder‘ is a reaction product of phthalic an
hydride and ethylene glycol.
r v
5. K'process for the preparation o‘fycatalysts
of -,.- cadmium nitrate‘ », and .one part or platinum - which comprises coating a carrier with catalyti
chloride .are'jground ‘together ‘in a ‘ball mill.‘ ,A
25 vehicleconsisting of a 15%. solution of'vpolystyrene
intolueneris added and the mixture is ground
untilsmooth,'diluted with toluene to the proper‘
consistency, and the mixture is sprayed=ontoY1500
parts or pumice of
average ‘v particle size of
‘the'catalyst/isw-placedyin a copper tube and heated
tog-25040016. while :a slowstream of hydrogen
vvi'Exdmple V11
35 parts bfvzincoxide are ground up‘ in a 100
cally active material and a poiystyrol -resfin,'an'd
then volatilizing the resin.
6. 'A' catalyst carrier coated ‘with a composi
tion containing a ?nely divided ‘ catalytically
active substance and a temporary binder selected
from a group consisting of unmodi?ed polyhydric
,alcohol-polybasic carboxylic acid“ condensation
products and styrol're'sins.
7. A catalyst carrier coated with a composition
containing a ?nely divided catalytically active
substance and a temporary binder comprisingv an
unmodi?ed polyhydric alcohol-'pol'ybuic car
boxylic acid condensation product.
ontolquartz of about 5-7 millimeters average
8. A'catalyst carrier coated with a composition
containing a ?nely divided catalytically active
substanceand va temporary binder comprising a
diameter. ~After evaporation of the solvent the -
parts of,'a :vehicle consistingo! a 15% toluene
solution of polystyrene.‘ ‘5' This mixture is sprayed
catalyst=>placedin a‘ tube‘ and heated to about
400°C.‘ The catalyst prepared' in this manner is,
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