June 3, 1941-
G. ROBERTS, JR
METHOD oF MAKING CATALYSTS
Filed July 18, 1938
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2,244,573
I
2 Sheets-Sheet 1
INVENTOR
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ATTORMEY
June 3, 1941.
G. RoBERTs, JR '
l.2,244,573> _
METHOD OF MAKING CATALYSTS
Filed July 18, 1938 '
2 Sheets-Sheet 2
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ATTOR
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Patented June 3, 19431»
2,244,573
UNITED STATES PATENT
FFICE
METHOD 0F MAKING (.'H‘YI‘ALYS'ISV
George Roberts, Jr., Montclair, N. J., assignor to
The M. W. Kellogg Company, New York, N. Y.,
a corporation of Delaware
Application July 18, 1938, Serial No. 219,931
4 Claims. (Cl. 252-253)
water from tank 5 and pumped by pump 6
through pipe 'i into the digester 3. Ten percent
My invention relates to a method of making
a catalyst and more particularly. a catalyst
4 excess dilute sulphuric acid is used.
adapted for useA in the catalytic conversion of
The dilution
' hydrocarbons, as for example, the conversion
is controlled by pump 8 which pumps water
of high boiling hydrocarbons to low boiling hy
drocarbons or the synthesis oi hydrocarbons from
through pipe ‘9 into the pipe l0 into which sul
phuric` acid passes from tank ¿i through pipe il.
The digester is vprovided with agitating means l2
mixtures of carbon monoxide and hydrogen.
Suitable catalysts for these operations are
'operated by any suitable means such as a motor
i3. The following reaction will take place be
'iinely divided'metals such as cobalt, nickel, iron,
- and the like, supported upon a suitable material 10 tween the thorium oxide and the sulphuric acid:
such as kiesel'guhr, silica or the like.
A nickel catalyst is cheaper per pound than
a cobalt cataylst, but more nickel catalyst is
When the solution is complete, 15` percent
required. All catalysts, after a period of use,
aqueous ammonia from tank lil is pumped
decline in activity and must be re-worked. In 15 through line l5 by pump i6 and agitation con
the case of a nickel catalyst, since greater
tinued to cause precipitation of thorium hy
amounts are necessary in a given operation andV
since its life may not be so long as cobalt cat
droxide as follows:
alyst, the re-working cost of a nickel catalyst is
greater.
20
‘
I have determined that a cobalt catalyst, hav
The slurry is then withdrawn from the digester
3 through pipe Il, controlled by valve i6 and
pumped by pump i9 through pipe 20 through a
plate and frame filterv press 2l. Ii desired,
ing approximately the following composition is,
from an economical point of view, taking into
consideration the cost of re-working, an excel
lent one. It is understood that it is given by
way of example and not by way of limitation,
since my method is applicable to any suitable
catalyst metal.
slurry may be diluted with water to wash it as
it is being introduced into the filter. For this
purpose, water pumped by pump 8 may pass
through line 9 past valve 24 through line 23
>
Weight (percent)
cobalt __________________ _; ___________ __
'I'horium oxide ________________________ __
Kieselguhr ___________________________ __
32.80
5.64
61.56
30
through pipe 22 into pipe 20.
`
The ammonium sulphate in solution is with
drawn from the filter through pipe 25. The
thorium hydroxide is withdrawn from the iilter
and conveyed by conveyor 26 operated by motor
One object of my invention is to provide a
2l into a digester 28. Nitric acid stored in tank
method of manufacturing a catalytic material in 35 29 iiows through pipe 3U controlled by valve
an economical and expeditious manner.3l and is diluted by water from pipe 32 controlled
Another object. of lmy invention is to provide
by valve 33v and passes through pipe 34 into the
a method of hydrolytically preparing a catalytic
digester 28, about ten percent excess of dilute
material.
nitric acid being` used. `The thorium hydroxide
Other and further objects of my invention will 40 and dilute nitric acid are agitated in digester 28
appear from the following description.
by agitating means 35 operated by motor 36
In the accompanying drawings which form
part of the instant specification and are to be
read in conjunction therewith and in which like
reierence'numerals are used to indicate like parts
in the various views.
Simultaneously with the solution of thorium
‘
Figure 1 is a diagrammatic view of a portion
of the apparatus capable of carrying out the
method of my invention.
Figure 2 is a diagrammatic view of the Yremain
ing portion of apparatus capable'of carrying out
the method of my invention.
until solution is elîectedas follows:- ‘
`
.
~
` oxide, metallic cobalt from hopper 31 is intro
duced past valve 38 into the digester 39 into
which is alsoy introduced 10 percent of 25 percent
nitric acid through pipe 40, the nitric acid being
taken from the .nitric acid tank 29 and being
diluted by water from pipe 32, valve 4l being
Referrlng now to the drawings, thorium oxide » ‘ openedand valve 42' being closed.
from hopper l is fed past valve 2 into va digester
3. Sulphuric acid from tank 4 is diluted with
The digester
39 is provided with agitating means 43 operated
by a motor 44.
2,244,573
' 2
which is `assumed to be as follows:
‘
acogfcHNose‘iHgo-l-acomos)2+2N0 .
pipe 18 to a settler 19 from which the washing
water is withdrawn through pipe 80. The washed
material is Withdrawn from the settler 19 and
conveyed through duct 80’ by augur 8l, operated
It is impossible towrite the exact equation be
by motor 82, to a drier 83, which may be oi' any `
cause other oxides of nitrogen may be given oí.
The oxides of nitrogen may be vented through
acid.
suitable construction. Air from any suitable
source passes through pipe 84, through pipe 85
controlled by valve 86 into a burner 81 which is
provided with gaseous fuel through pipe 88. The
fuel and air burn in chamber 89 and the products
'I'he excess acid in both the cobalt nitrate and
thorium nitrate solutions formed in digesters 39
of combustion pass through duct 90, through the `
drier and are withdrawn therefrom through pipe
In the digester 39 a reaction will take place,
pipe 44’ controlled by valve 45. If desired, the
oxides of nitrogen may be used to form nitric
and 28 respectively is neutralized with potassium
9|. Excess air may pass' through pipe 92 con- v
carbonate. The cobalt nitrate solution is with
trolled byyalve 93 to control the temperature.
drawn from the digester 39 through pipe 48 con 15 The temperature may be further controlled by
trolled by valve 41 and introduced into a tank
recycling the exhaust gases from the drier
48. 'I'he thorium nitrate solution formed in di
through duct 94 controlled by damper 95. ` 'I'he
gester 28 is withdrawn through pipe 49 controlled
dried material leaves the drier and passes to a vi
by valve 59 and passed through pipe 5l into
brating screen 96, the ñnes being withdrawn
the tank 48. A solution of potassium carbonate 20 through pipe 91 controlled by valve 98. The dried
is made in tank 52, potassium carbonate being in
particles are withdrawn through spout 99. These
troduced from a hopper 53 controlled by a valve
particles are then put in the catalyst chambers
54 and Water being introduced through pipe 55
where the carbonates are decomposed with hot
controlled by Valve 56. The tank 52 is provided
air as follows:
' ‘
with agitating means 51 operated by an electric 25
~ motor 58.
The potassium carbonate solution is
withdrawn from the mixing tank 52 through pipe
59 controlled by valve 68 and introduced in de
'The cobalt oxide is then reduced with hydrogen
sired amounts into the tank 48; Kieselguhr from
at 800° F'. as follows:
hopper 6I is introduced into the tank 48 through 30
valve 62, The tank 48 is provided with an agi
ating means 63 operated by an electric motor 64.
It is to be understood that any other suitable
support for the catalytic material may be em
ployed -such as ñnely divided clays, silica or the
The thorium oxide is not re'ducible at this
temperature so that the resulting catalyst will be
the kieselguhr containing metallic cobalt and
thorium oxide which seems to promote the action
of the cobalt catalyst.
‘'
like, which would be introduced from hopper 6l
As pointed out above, this catalyst is particu
instead oi’ the kieselguhr.
larly adapted for the synthesis of hydrocarbons
The potassium carbonate is introduced into a
from mixtures of carbon monoxide and hydrogen
tankv 48 through line 59. During the precipita
tion, the agitation is very thorough in order to 40 though it is to be understood that it may be em
ployedI for any suitable operation in which a ñnely
insure a uniform product. As will be clear from
divided metal deposited upon a carrier is desired.
the process hereinafter described, potassium car
Instead of cobalt, I may use nickel, iron or any
other suitable metal from which the nitrate may
bonate may be used for precipitation while con
suming only the cheaperI sodium carbonate. Po
tassium carbonate gives better results than sodi
sequently decrease -catalyst activity. In the tank
be formed by interaction with nitric acid and
which, further, is suitable as a catalyst, employ
ing the reactions analogous to those pointed out
above as will be readily understood by those skilled
in the art.
From the foregoing it will be clear that my
48 the following reactions occur:
process enables nitric acid to be used in preparing `
um carbonate and produces a more active cata
lyst. The reason `for this is unknown. While I do
not wish to be bound by any theory, this may be
because the sodium ions are adsorbed and sub
the initial solutions, while consuming only the
cheaper sulphuric acid. It is only necessary that
the acid will form a metallic salt which will react
.55 with a carbonate to form the metal carbonate for
decomposition to the oxide, followed by its reduc
The slurry formed in tank 48 is withdrawn
through pipe 65 controlled by valve 6‘6 and
pumped by pump 61 through a plate and frame
~filter press 68. The filtrate containing a solution
of potassium nitrate and potassium carbonate is
withdrawn from the ñlter 88 through pipe 69
tion to the metal.
-
'
l
I prefer to use nitric acid in the confection of
a cobalt catalyst because cobalt does not readily
_dissolve in sulphuric acid,'for example, and fur- »
ther, the presence of sulphur tends to poison the
' catalyst in a synthesis reaction.
Nitric acid is considerably more expensive than
for passage to the nitric acid and potassium car
sulphuric acid and potassium carbonate is more
bonate recovery operations shown- in Figure- 2.
The illter cake comprising a mixture of basic 65 expensive than sodium carbonate. 'I‘he nitric
acid and the potassium carbonate, are used to
cobalt carbonate (2C0CO3.3C0(OH)2) and thori
form intermediate products and I propose to re
um carbonate precipitated on the carrier, kiesel
guhr, is withdrawn from the ñlter and conveyed
cover these for reuse.
through duct 18 provided with a conveyor screw
The nitrate withdrawn from the filter 68
1| operated by a motorV 12 to a washer 13, water 70 through pipe 69 `contains an excess of potassium
being introduced into the Washer through pipe
The slurry is Withdrawn from the washer
carbonate in solution and potassium nitrate'.
This flows through pipe 69 to tank |00. Mag
nesium -carbonate slurry, previously separated in
the process, as will b_e hereinafter pointed out, is
through pipe 16 and pumped by pump llthrough 75
introduced into tank |08 through pipe - lill`
14 into a mixing chamber 15. 'I'he Washer may
be of any suitable type.
„
3
2,244,573
The magnesium carbonate, potassium carbonate
and potassium nitrate is withdrawn from tank |00
through ,pipe |02 and pumped by pump |03
from which it is withdrawn through pfipe |50 and
pumped by ‘pump |60 to pipe ISI, :to the nitric
acid storage tank 20 shown in Figure 1. The
sodium acid sulphate sludge is withdrawn from
retort |48 through pipe |64 and is discarded.
The filter cake from filter press |40 comprising
through pipe |04 into a mixer |05 provided with
agitati'ng means |06 driven by an electric motor
|01. Carbon dioxide from tank |00 is pumped
by pump |09 through pipe ||0 `and introduced
into the mixing chamber |05 which is maintained
under moderate pressure by back pressure con
trolled valve |||. The potassium is precipitated
magnesium carbonate and magnesium hydroxide
is withdrawn, through duct |62 and conveyed
through duct |03 for passage through _duct |20
with the magnesium carbonate filter cake from
filter |24 into the mixing chamber |3I.
The ñlter cakes are put in the solution with
carbon dioxide and water with the aid of vigorous
mechanical agitation. Water is introduced into
the mixing chamber |0| through pipe |55 and
carbon dioxide is passed into the chamber |31
through pipe |06 controlled by valve |51. The
following reaction will take place:
as a double salt according to the following reac
tion:
y
3 (MgCO3.3H2O) -|-2KNO3+CO2=~
‘
Mg ( Non) 2-1-2 (KHCO3~MgCOs .41120)
The double salt is insoluble.
'I‘he slurry formed in mixing chamber |05 is
withdrawn therefrom through pipe ||2 and
pumped by pump ||3 through filter press H0,
the filtrate vcontaining magnesium nitrate in so
lution which is withdrawn through pipe ||5 and
passed to mixer chamber H5. The ñlter cake
containing potassium acid carbonate- and mag
nesium carbonate is passed by conveyor screw
||1 through duct' ||0 inlto tank ||5 into which
water through pipe |20 is introduced. T-he solu
tion is heated by steam introduced through pipe
|21 to breakup the double salt and put potassium
carbonate into solution. The slurry is withdrawn
from .the tank H0 through pipe |22 and pumped
by pump |23 through ñlter press |20, filtrate
containing potassium carbonate in solution being
withdrawn through pipe |25 for pumping by
pump |20 through pipe |21 for passage to the
tank |00 through pipe 69. The filter cake con
taining the magnesium carbonate is withdrawn
20
SMgcOazMgmH)asino-estema:
4Mg(HCO3) 2+5H2O
The solution is withdrawn from the chamber
|0| through pipe |50 controlled by valve |69 and
passed into boiler |10 which is heated by steam
25 coil |1| to which steam is introduced through
pipe |12. The solution is boiled in boiler |10 with
'.the resulting precipitation of magnesium car
bonate in accordance with the following reaction:
30
4Mg (HCOa) 2+8H2O=4MgCOa3H2O+4CO2
The slurry containing the water and the mag
nesium carbonate in suspension is withdrawn
from the pump |10 through pipe |10 and pumped
35 by pump |14 through pipe |15 into a settler |16
from which water is decanted olf .through pipe
|11. The thickened slurry containing magnesi
from the filter |20 through duct |28 and con
um carbonate is withdrawn from the settler
veyed through duct |29 by conveyor screw |30
through pipe |18 and pumped by pump |10
to the mixer |3I. To the magnesium nitrate so
lution entering tank H5 is added a. solution of 40 through pipe |0| into the tank |00 as the mag
nesium carbonate previously separated in the
sodium carbonate withdrawn from tank |32
process.
through pipe |33 controlled by valve |34. The
By my method I am enabled to recover 95 per
magnesium nitrate and the sodium carbonate
cent of the potassium carbonate, about 90 percent
solution are agitated ‘by a mixer |35 operated by
of the magnesium carbonate and about 80 per-,
a motor |36. The following reaction takes place:
cent of nitric acid, based on the nitrate radical
present in the potassium nitrate.
It will be seen that I have accomplished the
objects of my invention. I have provided an ex
The slurry is withdrawnv from .tank ||6
through pipe |31 and is pumped by pump |38
through pipe |39 to the ñlter press |40, the fil
trate containing sodium nitrate being withdrawn
through pipe IM for passage to the Vevaporator
|42 in which the Walter is evaporated by heat
peditious method of preparing catalysts compris
ing ñnely divided metals supported upon a sili
ceous material such is kieselguhr, silica or the like
by hydrolytically depositing the metal carbonate
upon the support, which carbonate can be easily
‘ supplied through a coil |43 by means of steam 55 decomposed to the metal‘oxide which is subse
quently reduced to the metal.
introduced through pipe |44. Dried sodium ni
By means of my process, the only nitric acid
trate is conveyed through duct |45 by means of
required is to make up the loss in the form of
conveyor screw |46 operated by a motor |41 into
oxides of nitrogen and the only potassium car-‘
a retort |40 into which is introduced 95 percent
sulphuric acid from tank |49, .through pipe |50 60 bonate is that required to make up for losses.
My vappliance may be used for re-working an
controlled by valve |5| . The sodium nitrate and
old catalyst by dissolving the catalyst in nitric
the sulphuric acid react to form nitric acid as
acid to form the metal nitrate followed by proc
follows:
essing the same as in the case of a new catalyst.
65
It will be understood that certain features and
This reaction is weil known and has a broad com
sub-combinations are of utility and may be em
mercial background. The nitric acid is distilled
ployed without reference to other features and
from the retort |08 by means of heat supplied to
sub-combinations. This is contemplated by and
_a coil |52 by suitable heating medium or by ex
is within the scope of my claims. lit is further
ternal heating. Nitric acid vapors pass over 70 obvious that various changes may be made in
head through pipe |50 and are condensed in
details within the scope of my claims Without
condenser |55 to which a cooling medium is sup
departing from the spirit of my invention. It is,
plied through pipe |56. 'I'he condensate is
Withdrawn from the condenser |55 through pipe
therefore, to be understood that my invention is
not to be limited to the specific details shown
|51 and collected in an accumulator tank |50 475 and described.
vv4
2,24%,578
Having thus described my invention, I claim:
' l. A method of forming a catalyst comprising a
finely divided metal deposited upon a support in
cluding the steps of forming a solution oi'> the
desired catalyst metal in nitric acid comprising
a portion previously recovered in the process,
suspending a finely divided inert siliceous cata
lyst support in said solution, precipitating the
carbonate of the metal upon the Asupport and
forming a corresponding amount of potassium
nitrate by the addition of potassium carbonate
to the solution, separating the support together
with the precipitated metal carbonate from the
solution of potassium nitrate, drying and heat
ing said separated support and carbonate to de 15
compose the carbonate to form the oxide of the
metal in place upon the support, reducing the
potassium magnesium carbonate and heating the
mixture to decompose said carbonate to form
soluble potassium carbonate and insoluble mag
nesium carbonate, and separating and returning
the thus formed potassium carbonate for reuse in
said precipitating step.
3. A method of forming a catalyst adapted for l
use in the synthesis of hydrocarbons from mix
tures of carbon monoxide and hydrogen, said
catalyst comprising cobalt supported upon kiesel
guhr bearing a thorium oxide promoter which
includes the steps of forming a solution of cobalt
nitrate by the interaction of nitric acid and co
balt, simultaneously forming thorium hydroxide
by the interaction of thorium sulphate and am
monia, >reacting thorium hydroxide and nitric
acid to form thorium nitrate, agitating the solu
tion of cobalt nitrate and thorium nitrate with
oxide to form the metal in linely divided form
kieselguhr, precipitating cobalt carbonate and
disseminated upon the support, adding magne
sium carbonate to the filtrate containing potas 20 thorium carbonate from the agitated mixture
upon the kieselguhr forming a corresponding
sium nitrate to form magnesium nitrate, 'react
amount of potassium nitrate by addition of po
ing sodium carbonate with the magnesium ni
tassium carbonate, separating the kieselguhr,
trate to form sodium nitrate, reacting the sodium
and cobalt carbonate and thorium carbonate pre
nitrate with sulfuric acid to form nitric acid, and
25 cipitated thereon from the potassium nitrate so->
returning the nitric acid to the process.
lution, passing the potassium nitrate solution to
2. A method of forming a catalyst comprising
a finely divided metal deposited upon a support
including the steps of forming a solution of the
desired catalyst metal in nitric acid comprising
a portion previously recovered in the process, 30
a recovered nitric acid recovery operation, re
turning the nitric acid to the process, drying the
kieselguhr-cobalt carbonate-thorium carbonate
precipitate, heating the precipitate to decompose
suspending a ñnely divided inert siliceous cata
the thorium and cobalt canbonates to cdbalt ox
nesium nitrate and an insoluble magnesium po
in solution filtrate with sodium carbonate to form
ide and thorium oxide respectively, subjecting
lyst support in said solution, precipitating the
the mixture of metal oxides upon the kieseiguhr
carbonate of the metal upon the support and
to a reduction step to reduce the cobalt oxide to
forming a corresponding amount of potassium
nitrate by the addition of potassium carbonate 35 metallic cobalt, the thorium oxide being irreduc
ible under the conditions of the reducing step
to the solution, separating the support together
whereby the desired catalyst is formed.
with the precipitated metal carbonate from the
4. A method as in claim4 3 wherein said nitric
solution of potassium nitrate, drying and heating
acid recovery operation comprises agitating the
said separated support and carbonate to decom
pose the carbonate to form the oxide of themetal 40 potassium nitrate filtrate and magnesium car,
bonate in the presence of carbon dioxide to form
in place upon the'support, reducing the oxide to
magnesium nitrate and insoluble potassium mag
form the metal in ñnely divided form dissemi
nesium carbonate, separating the potassium
nated upon the support, adding magnesium car
magnesium carbonate from the magnesium ni
bonate and carbon dioxide to the solution con
taining potassium nitrate to form soluble mag 45 trate solution, reacting the magnesium' nitrate
sodium nitrate and magnesium carbonate, sepa
rating the solution of sodium nitrate from the
magnesium carbonate, evaporating the sodium
tion of magnesium nitrate, reacting sodium car
bonate with the magnesium nitrate to form sodi 50 nitrate solution to dryness, and reacting the so
dium nitrate with sulphuric acid to form nitric
um nitrate, reacting the sodium nitrate with sul
acid.
furic acid to form nitric acid, returning the nitric
GEORGE ROBERTS, JR.
acid to the process for reuse in forming a solu
tion oi the catalyst metal, mixing water with the
tassium magnesium carbonate, separating the
potassium magnesium carbonate from the solu
cnanFIcATE'oF CORRECTION. l.
Patent No. 2,gk14.,575.-
¿
June 5, 1914.1.
GEORGE ROBERTS, JR.
ItV~ is hereby certified that error appears, in the printed specification,
of the above nmnberetl- patent requiring correction as follows: Page 5, first
column, line 2.5, for “carbonate- and” 4read -- carbonate- -- --; page 14, » sec-,
ond column, line 25, claim 5, strike out- the colma after "kiese1guhr";' line
27, seme clainí, strike out "recovered" and insert the same'l before "nitric"
in> line 28, seme claim 5 ; 'and ~that: the said Lettere Patent should be` read
withS-thie correction therein that the same may' conform to the record of
'the case in the Patent office. .
signed and 'sealed this 1_ztn any or August, A. n. 19m.
’
(Seal)
'
Henry Ven Arsdale,
Acting Comi'seionergof Patents.