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Патент USA US2118829

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2,118,829
v' Pawns, 31, loss‘
‘'um'rso
7
" 5 STATES’
2.11m‘
PATENT
omcs
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PREPARATION OI‘ COBALT-'00P!“
,
CATALYSTS
H. Storch, Pittsburgh.
a-ignor to
Government, ‘oi theUnited States, asrcpre-‘
sentedbythesecretaryclthelnterlor
'
No Drawing. Application M 81, 1Q",
's?'lll N0. 134,.91
scrum;
(cits-s34)
-
‘
'(Grantednndertheactolll‘archl, 1m.”
amended
-
30, 1928; 8'10 0. G. 75'!) "
. The invention described herein may be manu
i'actured and usedby or for the Government for
governmental purposes, without the paymentto
me ct any royalty thereon.
"5
This invention relates to the oxidation of the
very simple procedure will restore its original
activity. This regeneration is accomplished by
passingaslow stream of air over the catalyst,._
whose temperature is maintained at 900°-1100‘_'
0., for a period oi’ about thirty minutes. Upon 5
subsequent reduction and use with water gas;
steam mixture, the catalyst, showed an activity
or a cobalt-copper catalyst for this and similar " identical with that of the original catalyst‘
reactions which will give high activity for ex
Slower heating of the cobalt carbonate-cop
‘ in. tended periods, and which is in the mechanically per oxide mixture, during the 1)
tion 01’ the 10
desirable form ‘of hard. porous granules.
catalyst, yields a powder which is not suitable for
Cobalt catalysts containing small amounts of. the rapid gas ?ow demanded by a space velocity
’ copper are knownto be very active at 300° to per hour of 15,000 for the water gas-steam mix
325° C. in catalyzing the water gas shift reaction ture. The probable'explanationof the di?er
, ence in mechanical properties of the catahrst l5_
carbon monoxide in-w'a’ter gas to carbon dioxide
by steam; and has for its object the preparation
.
co+mo=cm+m
when prepared by slow as compared with rapid
heating of the cobalt carbonate-copper oxide
_
The methods cry-preparation of such a catalyst j mixture, is as follows:
thus i'ar described in the literature involve iusion
*1: go ‘of the metal oxides in an oxy-hydrogen flame or
,
co-precipitation ‘as hydrated oxides from aqueous
_ solutions‘oi the nitrates. The former is an ex
5 pensive method for practical work; and the latter
does
not , readily yield mechanically Stable
The formation of intermediate compounds
which may be represented by the formula 20
(Cook-(Cocoa), results in a ‘su?iciently low
melting compound to yield the observed sintering
phenomenon; for it is conceivable that such in
termediary compounds may decompose below
‘
their melting points, and hence rapid heating 25
‘I have found that ii’ a mixture 01' cobalt car 1 would result in sintering whereas a slow rate of '
bonate with small amounts, for example, between
5 percent and 25 percent. of copper oxide is
rapidly heated within three minutes or less from '
so room temperature to a temperature between 900°
- and 1100' C. a sintered, pumice-like mass of
granules is obtained. This product has excellent
heating may‘ give ample time for complete de
composition to occur before the melting point is
reached.
-
' Suitable precautions are taken to avoid sinter- 30
ing‘ of the catalyst during reduction. Such pre
cautions preferably are taken by so conducting ,
mechanical properties which permit prolonged a the reduction that sintering temperature cannot
use without appreciable spelling. It isalso a . occur.
.
very active catalyst when properly reduced and
subsequently protected from poisoning. particu
larly poisoning with sulfur or sulfur compounds.
An example of theactivity of this‘catalyst in
practical me is as follows: '
40
’
I
I
Water gas was made by-the reaction of Pitts
In the preferred practice of my invention
to prevent large uncontrollable increases in tem- 35'
perature during reduction it is usually desirable
todilute the reducing gas with nitrogen or- other
inert gas. For example: a satisfactory mixture
would be 5 volumes of hydrogen or of water gas
burghnaturalgas
This gascontained plus 95 volumes of nitrogen. This reducing mix- 40
about '72 percent Hz, 21' percent 00, 3 percent ture is passed over the granules of catalyst pref
00:, 2.6 percent N2, 1 percent CH4 and 0.5 percent\ ,erably' contained in a copper lined vessel, and
0:. This'gas was mixed with four volumes or heated to not over 500° C. and preferably to about
‘>
"
48v steamandpassedthroughamesh granules oi'the 200-300‘I C.
cobalt-copper catalyst prepared ‘as described ' 'During reduction the gray colorof the unre- 45
above, at 310' C. and at a ‘space velocity per hour
‘otmofdrywater'gas ora spacevelocityper
hour of 15,0000! the water gas-steam mixture.
60 The carbon monoxide content oi'the oil-gas was
duced granules changes to a "copper'? .color', and
the mechanical properties of the granules are
essentially. the same ‘as thoseof the unreduced
material. After poisoning occurs ‘the regenera- ‘50
0.2 percent and the methane content about 2 per- _ ' tion of the spent catalyst by oxidation and~ re- ’ cent. during a period of 100 hours operation. '
duction, results in a considerable decrease in
I have further foi'md that when for sny'reason
the catabst should become poisoned-as for ex
ll ample,byimplu'itiesintroducedbythe-steam; a
mechanical stability of the catalyst. It‘ is there
fore desirable to avoid poisoning by the introduc
tion of a purifying system; The latter may con- as
2,1185”)
2
4. J'I‘haimprovedcatalyst obtained by quick
sist of lead chromate deposited on pumice, active
charcoal, copper turnings kept at 500° 0.,‘ etc.
heating a ‘mixture of cobalt carbonate in major
amount and copper oxide-in" minor amount by
the method of claim 2, said catalyst being in
1. A method for the preparation of cobalt
ccpper catalysts which comprises vheating .up
mixtures of cobalt‘ carbonate and copper oxide,
the formsof a sintered, pumice-like mass of gran
ules, capable of being reduced by reducing gases,
at a rapid rate, that is, about 350° 0. per minute capable-of ‘prolonged use without appreciable
spalling, and, capable of being rapidly regener
to a temperature ‘between 900° and 1100° Q.
2. A method for the preparation‘ of cobalt ' ated, when poisoned, by heating to between 900°
10 copper catalysts which ‘comprises heating up and‘llOO’ C. ina slow'streamof an oxidizing gas,
mixtures of cobalt carbonate and copper oxide, substantially as described.
10'
'5. The improved catalyst obtained by quick
, at a rapid rate, that-is, about 350° C.'per minute
heating and reduction of ‘a mixture of cobalt car
bonate in major amount and copper oxide in
to a temperature between 900° and 1100° C.; and
subsequently reducing the resulting mixtures of
minor amount by the method of claim 3, said 15
>
3. A method for the regeneration of poisoned catalyst being in the .form of a sintered pumice
cobalt-copper catalysts prepared as described in. like mass of granules, capable of prolonged use
without appreciable spalling, catalyticaliy very
claim 2. which comprises heating these at a tem
perature between 900° and, 1100° C. in a slow active at a temperature near 310° C., and capable
of being regenerated, when poisoned, by oxida
20 ‘stream of an oxidizing gas vfor a-period of time
su?icient (usually about thirty minutes) to re—' tion at a temperature of about 900'" to‘ 1100° C.
_ > .
v
move the poisons; and subsequently reducing the followed by reduction.
'
HENRY H. .STORCH
resulting mixtures of oxides with reducing gases.
oxides with reducing gases.
CERTIFICATE OF
Patent No. 2,118,829.
CORRECTION.
_
,,
May 31, 1938.“
'
' HENRY I-l‘. STORCH.
_ It is hereby certified ‘that error appears‘ in‘. the printed specification
of the above numbered patent requiring correction ‘as follows: Page 2, first
column, line 18, claim}, and second column, line Li, claim 14., for theclaim
reference numeral "2" read 1; and line 15, claim- 5, for ."5" read- 2, and.
that the said Letters Patent should beread with these corrections therein
that the same may conform to the record of the case in the Patent Office.
Signed and sealed this 5th‘ day of July, A.D>. 195B,
‘ ‘
Henry Van Ar sdale,
"Acting Commissioner of Patents.
2,1185”)
2
4. J'I‘haimprovedcatalyst obtained by quick
sist of lead chromate deposited on pumice, active
charcoal, copper turnings kept at 500° 0.,‘ etc.
heating a ‘mixture of cobalt carbonate in major
amount and copper oxide-in" minor amount by
the method of claim 2, said catalyst being in
1. A method for the preparation of cobalt
ccpper catalysts which comprises vheating .up
mixtures of cobalt‘ carbonate and copper oxide,
the formsof a sintered, pumice-like mass of gran
ules, capable of being reduced by reducing gases,
at a rapid rate, that is, about 350° 0. per minute capable-of ‘prolonged use without appreciable
spalling, and, capable of being rapidly regener
to a temperature ‘between 900° and 1100° Q.
2. A method for the preparation‘ of cobalt ' ated, when poisoned, by heating to between 900°
10 copper catalysts which ‘comprises heating up and‘llOO’ C. ina slow'streamof an oxidizing gas,
mixtures of cobalt carbonate and copper oxide, substantially as described.
10'
'5. The improved catalyst obtained by quick
, at a rapid rate, that-is, about 350° C.'per minute
heating and reduction of ‘a mixture of cobalt car
bonate in major amount and copper oxide in
to a temperature between 900° and 1100° C.; and
subsequently reducing the resulting mixtures of
minor amount by the method of claim 3, said 15
>
3. A method for the regeneration of poisoned catalyst being in the .form of a sintered pumice
cobalt-copper catalysts prepared as described in. like mass of granules, capable of prolonged use
without appreciable spalling, catalyticaliy very
claim 2. which comprises heating these at a tem
perature between 900° and, 1100° C. in a slow active at a temperature near 310° C., and capable
of being regenerated, when poisoned, by oxida
20 ‘stream of an oxidizing gas vfor a-period of time
su?icient (usually about thirty minutes) to re—' tion at a temperature of about 900'" to‘ 1100° C.
_ > .
v
move the poisons; and subsequently reducing the followed by reduction.
'
HENRY H. .STORCH
resulting mixtures of oxides with reducing gases.
oxides with reducing gases.
CERTIFICATE OF
Patent No. 2,118,829.
CORRECTION.
_
,,
May 31, 1938.“
'
' HENRY I-l‘. STORCH.
_ It is hereby certified ‘that error appears‘ in‘. the printed specification
of the above numbered patent requiring correction ‘as follows: Page 2, first
column, line 18, claim}, and second column, line Li, claim 14., for theclaim
reference numeral "2" read 1; and line 15, claim- 5, for ."5" read- 2, and.
that the said Letters Patent should beread with these corrections therein
that the same may conform to the record of the case in the Patent Office.
Signed and sealed this 5th‘ day of July, A.D>. 195B,
‘ ‘
Henry Van Ar sdale,
"Acting Commissioner of Patents.
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