Patented June 13, I933v 1,913,405v

UNITED STATES PATENT OFFICE -

VIRGIL E. MEHARG, OF BLOOMFIELD, NEW JERSEY, AND HOMER ADKINSyOF MADISON,
WISCONSIN, ASSIGNORS T0 BAKELITE CORPORATION, OF NEW YORK, N. Y., A COR
PORATION OF DELAWARE '

FOBMALDEHYDE SYNTHESIS AND CATALYST

_No Draw ing. Application filed July 31, 1931. Serial No. 554,378.
This invention relates to the production of the following claims taken in conjunction
formaldehyde by the catalytic oxidation of with the accompanying speci?cation which,
methanol, and to the catalyst which is used. however, must be taken as merely illustrating
Various catalysts such as copper and silver the invention and in no way limiting it- to
gauze have been suggested for use in this re the speci?c embodiment about to be described. 65
action but they are not desirable because of The catalyst is a mixture of molybdenum
the relatively large amount of by-products oxide and one or more of the oxides of iron,
which they produce. Other catalysts have lanthanum, thorium, neodymium, zinc, and
been suggested but they are usually of a type tin, the mixture of molybdenum oxide and
10 which have very little inherent strength and ferric oxide being the preferred catalyst. 60
therefore must be mounted on a support. The invention will therefore be described in
Such catalysts have a relatively short life be connection with a catalyst containing only
cause of their fragility. iron and molybdenum oxides.
The catalyst which forms the subject of the In making the catalyst, a dilute water so
present invention is highly satisfactory from lution of a molybdenum salt, such as ammo 65
a practical standpoint in that it combines nium molybdate (hepta-molybdate) and an
long life with a high yield of formaldehyde, iron salt such as ferric chloride, are prepared.
the yield being based both on the weight of The two solutions are mixed and a dense yel
formaldehyde produced per hour and the low precipitate of the oxides of molybdenum
20 weight of formaldehyde produced from an and iron is obtained therefrom Which'is thor-_ 70
equivalent _m_olecular weight of methanol. oughly washed. The precipitate is then ?l
The catalyst has relatively great inherent tered on a vacuum ?lter using a high vacuum,
strength so that it may be used by itself in and a relatively high pressure is -put on the
the catalytic chamber, that is, it does not have precipitate to compact it as it is being ?l
25 to be supported. Because of its strength, it tered. The resulting product is a fairly dense 75
does not erode so quickly as do similar cata but somewhat porous mass which still con
lysts and even though there be a slight tains a considerable amount of moisture. It
amount of erosion, such a large amount of is thereafter thoroughly dried,.so much (of Y
catalyst can be packed in a given space, that the water being taken off as will evaporate in
30 the catalyst lasts for an exceedingly long an oven maintained at substantially 100 C. 80
time before the catalytic chamber has to be in from 1 to 3 days. '
opened to renew the supply of catalyst. The The catalyst is a mixture of the oxides of
iron and molybdenum, the molybdenum oxide
catalyst also operates at a relatively low tem
perature. with many advantages. namely that being the speci?c catalyst and the iron oxide
35 the catalyst is not so likely to be killed by being the promoter. For commercial use un 85
high heating, cheaper materials may be used der the conditions later to be set forth, the
in the construction of the apparatus because catalyst preferably contains molybdenum
they do not have to withstand such high equivalent to from substantially 60% to sub
temperatures, and there-is less tendency for stantiallv 99% by weight of molybdenum tri
40 the formaldehyde to decompose after it leaves oxide. If much more than 20% by .weight of 90
the catalytic chamber. In addition to these iron oxide is used, the catalyst has a tendency
advantages, the catalyst reacts all of the to form by-products and waste the methanol.
methanol converting substantially all of it If less than 5% of the iron oxide is used, the
into formaldehyde, with a very small per catalyst does not operate so quickly as is
4.5 centage of by-products, thus eliminating all deemed desirable. From 8% to 20% by 95
of the recovery processes which heretofore weight of iron oxide (Fe2O,) is deemed the
have of necessity been used to recover the un optimum composition.
reactcd methanol. The catalyst appears to be a precipitate
These and other objects and features of caused by the addition of a positive and'a
50 the invention will more fully appear from negative colloid. Its character as revealed 100
 2 1,913,405
by X-ray study, shows that it lies on the bor should be decreased, and with a more effi
der-line between a crystalline and an amor ciently cooled chamber the methanol may be
phous compound because the X-ray plates increased. If the reactants are mixed in the
show the darkening effect characteristic of an above stated proportions and are then passed
amorphous material while there are also de? through the catalytic tubes so that the vapors
nite lines which indicate a crystalline struc are in contact with the catalyst for approxi 70
ture. mately .01 to .03 of one second and the tem
The dried catalyst is a hard but hi hly perature of the chamber is maintained at ap
porous light yellow homogeneous mass hav
10 ing sufficient inherent strength to support it proximately 250 C., all of the methanol can
be reacted with only one passage through the 76
self in the catalyst chamber independently of catalyst, even though the temperature is
extraneous internal support. The solid mass relatively low, and an e?iciency of substan
prepared as above described, and consisting tially 95% may be obtained'if desired, that is
throughout of a homogeneous mass, is broken substantially 95% of the methanol which is
15 up and preferably screened through a 5 to 10 fed into the catalytic chamber is obtained as 80
mesh screen which gives pieces of effective formaldehyde in the finished product. This
size to be used in a catalytic tube. For prac is not only a higher e?iciency than has pre
tical use the catalytic tube is provided at one viously been obtained but is a complete con
end with a screen through which the pieces version of the methanol which is usually de
20 of catalyst will not pass, then the catalyst sirable because it eliminated the necessity of 85
is placed in the tube to, a depth of from 6 to recovering unreacted methanol from the
12 inches after which a pre-heater, of a heat product. If it is desired that the ?nished
conducting metal, such as steel balls, is placed product contain methanol. in addition to
25
on top of the catalyst. Thev larger the pieces formaldehyde, it is possible to accomplish
of catalyst the greater the quantity of cata this with less than a 5% loss of methanol, by
lyst placed in the tube because there is less changing the conditions under which the re
effective catalyst surface; also the greater the action is carried out,_for instance by lower
effective area of catalyst, the faster the vapors ing the temperature of the reaction chamber
can be passed through the catalytic chamber, or by increasing the rate of flow of the va
but the additional heat due to the increased pors. I - 95
rate of reaction must be dissipated. The It should be distinctly understood, how
larger pieces of catalyst are preferred to the ever, that although certain operative condi
smaller piecescbecause they do not pack to tions have been stated, the temperature, time
gether so closely and, the vapors can pass of contact, and composition-of the reacting
through the tube more easily, and also be mixture may be varied within rather wide
cause, as the catalyst erodes, the ?ne dust has limits, and that the above description is given
a greater tendency to pass out of the catalytic only by way of example. For instance, the
chamber rather than remain in the chamber bath temperature may vary from 25 to 50
to choke it and to prevent the passage of va C. or more on either side of the normal oper
pors. It should be understood, however, that ating temperature of 250 C. Furthermore, '
in any case the surface area of the catalyst the percentage of methanol in the entering
should be su?icient to react all of the meth vapor may vary anywhere from 5% to 12% y
anol. -
and the time of contact of the vapors with
With this catalyst, the conditions of work the catalyst may vary from .005 seconds to
ing the process may vary within rather wide 0.5 seconds without appreciably a?ecting the 110
limits, and this is a great advantage in practi yield. As previously stated, however, a d
cal operation because the process is thereby combination of operating conditions is; ?rth
rendered very flexible. The reaction takes maintained at 250 C., reactants consist of
place in the vapor phase, and the vapors usu from 8% to 10% by weight of methanol va
ally enter the preheating portion of the heat por with 90% to 92% air, reactants in contact 115
er at substantially room temperature. Air with catalyst for substantiall .01 to substan
is most frequently used to supply the oxygen tially .03 of one second, cata yst substantial
necessary for the reaction.~ The methanol is 1y 8 mesh indiscriminately packed in tubular
vaporized in any suitable manner. The va catalytic chambers to a depth of substantial
pors entering the pre-heater contain substan ly 9 inches Under these conditions, sub 120
tially from 8% to 10% by weight of methanol stantially 95% of the methanol is converted
but, as previously stated, this is subject to into formaldehyde, and substantiall 5% of
wide variation. This percentage of meth by-products, consisting of CO and C 2, and a
C)
anol is preferably used with a catalytic trace (.0O1.01%) of organic acid, are
chamber consisting of several parallel pipes formed. The by-products do not contami 25
because it has been found relatively easy to nate or foul the catalyst which will operate
extract the heat generated by the mixture of satisfactorily for from 6 to 18 months with
air and methanol containing this percentage out renewal as substantially the only condi
_ of methanol vapor. With a less efficiently tion which will render the process ineffective
cooled chamber, the percentage of methanol is the gradual erosion of the catalyst with the 1.9
 1,913,405 3
consequent clogging of the tubes of the point is reached where the proportion of
catalyst chamber. It takes a relatively long methanol to oxygen is so large that the con
time for the tubes to clog, however, because ditions in the catalytic chamber are not
the relatively large. pieces of the catalyst and strongly oxidizing or the heat developed can
the relatively large spaces between them en not be dissipated, it being understood that 70
able the dust formed by the erosion of the if a larger percentage of methanol is used,
catalyst to pass out of the chamber, and as there is a proportionately larger amount of
there is such a great quantity of the catalyst heat generated and, as this must be removed,
in the permissible chamber space compared a greater cooling will have to be effected else
10 to the quantity of active catalyst which the catalyst will become too hot and will burn 75
could be put into the same space if it had to out. The greater the percentage of iron oxide
be mounted on a1 support, the operation can in the catalyst, the more quickly will the
be continued for an exceedingly long time methanol be converted into formaldehyde .
without stopping to renew the catalyst. and by-product, but also, the greater will be
15 Since all the methanol can be and usually 18 the quantity of the by-product. The greater 80
reacted, there is no costly or troublesome the percentage of molybdenum oxide - the
recovery of, methanol, and the process is very slower will be the conversion and the less will A
inexpensive to operate. All previous com be the quantity of by-product formed. It is
mercial catalysts have produced. a relatively thereforeto be understood that it is recog
20 large amount of acid even with an incom nized that many modi?catioins of the cata
plete conversion of the methanol to formal lyst and process may be made and it-is de~
dehyde. In many cases this acid runs as sired that the invention is to be construed
high as 1% and is highly objectionable. as broadly as the claims taken in.~conjunc_
lVith the herein described catalyst operated tion with the prior art, may allow.
25 in the proper manner, the acid almost never We claim: 90
runs above .01% and is consistently below 1. A catalyst for the oxidation of methanol -
that ?gure, quite frequently being as low as to formaldehyde, containing iron and molyb
001%. - denum, the iron and molybdenum being in the
During the process the catalyst, so far as same proportions as would be present in an
30 the eye can see, changes only slightly in color. iron oxide, molybdenum trioxide mixture 95
At the start of the reaction it is a light yel containing from substantially 40% to 66%
low and on continued operation it becomes of molybdenum by Weight. ,I i
more white. X-ray examination of the used 2. A catalyst for the oxidation of methanol
catalyst discloses a slight crystalline growth to formaldehyde including a porous mass of
35 but neither change seems to affect the cata precipitated iron and molybdenum com 100
' lyst which is extremely rugged. pounds, the iron and molybdenum being in
From the foregoing explanation of the in the same proportions as would be present
vention, it will be understood that many in an iron oxide, molybdenum trioxide mix
changes may be made in operating conditions. ture containing from substantially 40% to
40 The exact conditions of commercial operation 66% of molybdenum by weight. _ ' 105
are most likely to be determined by the ma 3. A catalyst for the oxidation of methanol
terials available for the manufacture of the to formaldehyde, containing iron oxide and
apparatus and-the materials which cool the molybdenum oxide and having sufficient in
catalytic chamber, or the design of the cham herent strength to maintain its form.
her for the extraction of heat._ In general, 4. A catalyst for the oxidation of methanol 110
it may be remarked that the faster the re. to formaldehyde consisting of a homogeneous
actance and passed over the catalyst, the catalytic mass containing molybdenum oxide
greater is, the amount of formaldehyde and iron oxide. . ' .
formed per hour up to a point where the 5. A catalytic unit for the oxidation of
50 vapors do not remain in contact with the methanol to formaldehyde consisting of a 115
catalyst long enough for the complete conver homogeneous mass containing the catalysts
sion of the methanol. The higher the tem molybdenum oxide and iron oxide, the latter >
perature, the more complete will be the con vconstituting not more than 20'per cent of the "
version of the methanol but the greater will mass.
55 be the loss in by-products. The longer the 6. A catalyst for the oxidation of methanol ' 120
time that the reactants are in contact with to formaldehyde consisting throughout of a '
the catalyst. the more complete will be the homogeneous mass containing the catalysts
conversion of the methanol and, therefore, as molybdenum oxide and iron oxide.
the catalyst erodes. the speed of the gases 7. A catalyst for the oxidation of methanol
should be slightly decreased or else the tem to formaldehyde consisting of individual 25
perature of the catalvtic chamber should be units of a homogeneous'catalytic mass con
slightly increased. The greater the-percent taining molybdenum oxide and iron oxide.
age of methanol in the reactants, the greater 8. A catalyst for the oxidation of methanol
will be the production of formaldehyde per to formaldehyde consisting of a homogeneous
65 hour for the same time of contact until the mass containing the catalystsfmolybdenum 130
 4 . 1,913,405

oxide and iron oxide and independent of ex

traneous internal support.
9; A process of producing formaldehyde
which includes the step of passing a gaseous
mixture containing methanol and oxygen in
contact with a heated catalyst containing
molybdenum oxide and iron oxide and hav_
ing sufficient inherent strength to maintain
its form.
10 10. A process of producing formaldehyde
which includes the step of passing agaseous
mixture containing methanol and oxygen in
contact with a heated catalyst consisting
throughout of a homogeneous mass contain
15 ing molybdenum oxide and iron oxide.
11. A process of producing formaldehyde
which includes the step of passing a gaseous
mixture containing methanol and oxygen in
contact with a heated catalyst consisting
20 throughout of a homogeneous mass contain
ing molybdenum oxide and an oxide of at
least one of the group consists of, iron,
lanthanum, thorium, neodynium, zinc, and
tin. '
25
12. Process of producing formaldehyde
which comprises passing a gaseous mixture
of methyl alcohol and oxygen in contact with
a catalyst consisting essentially of an oxide
of molybdenum and an oxide of iron, the lat
30 ter constituting not more than twenty per
cent of the catalyst. '
13. Process of producing formaldehyde
which comprises passing a gaseous mixture
containing methyl alcohol and oxygen in con
tact with a catalyst consisting essentially of
an oxide of molybdenum and an oxide of
iron at atemperature maintained at approxi
matcly 250 C.
40
14. Process of producing formaldehyde
which comprises passing a gaseous mixture
containing methyl alcohol and oxygen in
contact with acatalyst composed of oxides
obtained as a precipitate from solution of a
molybdenum and a salt of one of the metals
46
of the group consisting of iron, lanthanum,
thorium, neodynium, zinc and tin. _
In testimony whereof, we a?ix our signa
tures. '
VIRGIL E. MEHARG.
50
HOMER ADKINS.