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Патент USA US2110881

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2,110,881
’ Patented Mar. 15,
UNITED STATES
PATENT OFFICE
2,110,881
MANUFACTURE OF CATALYTIC MATERIAL
SUITABLE FOR THE VAPOR PHASE HY
DRATION OF OLEFINES
Waiter Philip Joshua, Cheam, Herbert‘ Muzzle
ton Stanley, Tadworth, and John Blair Dymock,
Sutton, England
No Drawing. Application May 14, 1935,
Serial No. 21.478
10 Claims. (Cl. za-zsw)
This invention relates to the manufacture of
catalytic material suitable for the vapor phase
hydration of ole?nes by steam' under pressure.
In the hydration of ole?nes there are certain
6 limitations from the technical standpoint. In
particular the use of certain metals in the con
struction of the apparatus employed should be
avoided either because they are liable to be at
tacked, especially if a liquid acid catalyst is used,
10 or because they themselves exert an undesired
catalytic effect. The employment of solid cata
lysts is preferable to liquid catalysts not only be
cause‘ of the corrosive action of the latter but
also because of the di?iculty of maintaining liq
15 uid catalysts at constant catalytic strength if
continuous operation with constant yield is
tion or during the manufacture of the pellets,
tablets or other pieces. The organic constituent
may be a water soluble substance and be incor
porated in aqueous solution with the catalytic
material, or it may be incorporated as a disper
sion in water, the water serving to ensure thor
ough dispersion and also functioning during the
subsequent carbonization step to ensure penetra
tion of the carbonizing action to the centre of
each pellet or other compacted piece of the com 10
position. In compounding the above-mentioned
ingredients a binder may be employed in an
amount up to 20 per cent. of the dry weight of
the catalytic material, preferably a drying oil
such as linseed oil or tung oil that also supplies 15
carbonaceous residue when carbonized under
certain circumstances as when used in conjunc
aimed at. On the other hand solid catalysts
are liable to be detrimentally affected as to their ‘ tion with phosphoric acid as hereinafter men
physical condition by steam under pressure and tioned. As an alternative to incorporation of
26 if they disintegrate their catalytic efficiency is
reduced and dif?culties in plant operation are
encountered.
It is therefore the principal object of the pres
ent invention to provide a catalytic material for
a 25 hydration of ole?nes that will maintain its phys
ical characteristics as a solid and its efficiency
as a catalyst for long periods of continuous use
under the conditions required in olefine vapor
the water or aqueous solution or dispersion con
20
talning the organic constituent at one stage and
of the oil at a second stage these stages may be
combined by making an emulsion of the oil with
the water or aqueous solution. If desired a dis
persion accelerator such as acetone or other water 25
soluble organic compound may also be employed.
A still further object is to provide a vapor
phase olefine hydration catalyst having the
physical properties of non-corrosiveness and sus
tained structural stability under operating con 30
More speci?cally stated, an object of the pres
ent invention is to provide a hydration catalyst .ditions combined with the catalytic advantages
of containing acid radicals especially phosphoric
so compounded that while under operating con
ditions it is substantially non-corrosive to metals, acid radicals and preferably containing both me
especially steel. From this aspect the catalytic tallic phosphate and phosphoric acid, since such
35 composition provided by the present invention is catalytic material is highly satisfactory for con 35
one in which has been incorporated during itsv tinuous vapor phase hydration of ole?nes on a
manufacture a constituent or constituents that commercial scale when it can be used without
render the ?nished catalyst non-corrosive under attacking the reaction plant and without itself
phase hydration processes.
30
operating conditions.
40
,
A further object is to provide a hydration
catalytic composition in solid form that has
disseminated throughout each pellet granule or
‘other solid piece of the material a constituent
that confers mechanical stability on the catalyst
under operating conditions.
A still further object of the invention is to
provide a solid catalytic material in the form of
tablets, pellets, or other solid pieces compacted
‘ in a press or by extrusion or otherwise and con
50 taining throughout their structure a mechanical
ly stabilizing carbonaceous skeleton. More par
ticularly the mechanically stabilizing carbona
ceous skeleton is produced in situ by carboniza
tion of an organic constituent incorporated in
55 the actual catalytic material during its prepara
deteriorating in structural and catalytic prop
erties.
The invention is particularly'but not exclu
40
sively applicable to the preparation of olefine hy
dration catalysts compounded from a compound
or compounds of uranium, boron, copper, iron,
manganese, cobalt, calcium, barium, strontium 45
and magnesium, wherein the amount of phos
phoric acid employed in their preparation is in
excess of that required to form the orthophos
phate or orthophosphates of the elements in
volved.
The above-mentioned and other objects and
features of the present invention will be ap
parent from the following description of two
examples of the manner in which the invention
is carried into effect.
50
55
2
2,110,881
However before describing these examples it
may be pointed out that the vapor phase hy
dration of ole?nes by means of water vapor
negligible quantities of polymers and acetalde
using solid catalysts containing metal phos
phates and excess phosphoric acid stabilized'by
hyde were formed. After a prolonged period of
operation the fragments of catalyst were still
the residue of certain‘ carbonaceous materials
admixed and carbonized is disclosed per se in the
speci?cation of our co-pending application Ser.
the reaction vessel showed no signs of corrosion.
No. 707,416.
10
Example I
A catalytic composition was ?rst prepared by
making a suspension of manganese carbonate
and boric anhydride in water and adding thereto
15 phosphoric acid (as HQPOO, these constituents
being in the ratio of 3.2 mols of the acid to 1
mol. of the carbonateand 0.5 mol. of the boric
anhydride whereby there is formed a complex of
manganese phosphate and boron phosphate and
20 phosphoric acid in excess of that required to form
the normal phosphates of the boron and man
ganese. This solution was evaporated down to
dryness and broken into small pieces and heated
at 250° C. for 2 hours. The dried pieces were
25 then ground to a fine powder and graded and
the graded powder was again dried at 250° C. for
2 hours. 600 grams of the dry powder were then
mixed intimately with a solution of 6 grams of
sucrose in 40 grams of water, and then with 70
30 grams of tung oil dissolved in an equal volume
of petroleum ether.
Instead of making a dry
powder by heating before adding the sucrose a
certain amount of water (as hereinafter speci
fied) might be left in the mass during the evap
35 oration stage but the advantage of thoroughly
drying before adding the sucrose solution is that ‘
the minimum amount of water contained in the
mass before the ?nal heating or carbonization is
then more accurately known and moreover the
40 complete drying facilitates the grinding and
grading.
It 'has been found that in order to
catalytically active and structurally stable and
Example II
A catalytic composition was prepared in the
manner described in Example I but in the ratio
of 2.8 mols of phosphoric acid (as H3PO4) to 1
mol. oi’ manganese carbonate and 0.5 mol. of
borlc anhydride.
_
with 1000 grams of the dry graded powder was
intimately mixed first a solution of 10 ‘grams of
sucrose in 60 grams of water and then 130 grams
of tung oil dissolved in an equal volume of petro
leum ether. After a thorough mixing of the re
sulting mass 50 grams of water were added. The
added water is required in this case because the
acidity of the catalytic material is less than in
Example I. The mass was then extruded through
a die 6 millimetres in diameter and was cut into
short lengths and heated slowly to 250° C. at
which temperature it was maintained for 2 hours
to ensure thorough carbonization throughout the
body of each fragment. Under the same condi~
tions of hydration of ethylene as in Example I.
the alcohol output per litre of catalyst was 300 30
grams per hours in the form of a 6.1 per cent.
aqueous distillate. After a prolonged period of
operation the catalyst was still catalytically ac<
tive and structurally stable and the reaction ves
sel showed no signs of corrosion.
After forming the constituents into compacted
piece as by tabletting or by extrusion and cutting
into short lengths, the compacted pieces may be
matured for several hours by heating at a tem
perature of only about 100° C. to 150° C. before
subjecting them to the higher temperature men
secure the most thorough carbonization the
amount of water present should not be less than
tioned. namely 250°_ C.
2 per cent. by weight of the dry catalytic mate
rial. The amount of water added in this example
is of course capable of various modi?cations.
is in excess of 2 per cent. and the resulting mass
55
hourly output of alcohol was 410 grams in the
form of a 7.2 per cent. aqueous condensate. Only
The procedure set out in the above examples
For example, although the employment of tung
is ?t for a moulding operation, preferably ex
oil in petroleum ether has been mentioned as the
binder which serves also as a provider of residual
trusion. _ Obviously, however, the mass instead of
carbon during carbonization, we may employ lin
being extruded might be tabletted in which case
the water and oil content must be adjusted
(somewhat less than for extrusion) to facilitate
that operation. An excess of water would merely
entail wasteful evaporation. A knowledge of the
appropriate amount for each circumstance is
seed oil instead of tung oil or a mixture of lin
seed oil and tung oil which are mentioned in 50
our copending application Ser. No. 692,222 or a
vegetable non-drying oil such as castor oil or rape
oil, or a purified animal oil particularly an oil
containing unsaturated radicals such as whale
oil, or an aliphatic alcohol or acid of high molec
ular weight such as cetyl alcohol or stearic acid
readily acquired by experience.
The resulting
mass in the present instance was extruded
through a 6 millimetre die and cut into rods
about 10 millimetres long. The resultant short
rod-like catalytic material was then again heated
60 slowly to 250° C. and maintained at that tem
perature for two hours to effect carbonization.
The catalytic material so prepared was very hard
and durable and was physically homogeneous,
the body of each piece being black in appear
65 ance through-out due to the skeleton of carbon
residue resulting from the carbonization of the
sucrose and the tung oil. Vapor phase hydra
tion of ethylene by the use of this material was
carried on continuously in a steel vessel by pass
ing ethylene and steam in the ratio of 3 mols to
1 mol. under a total pressure of 40 atmospheres
. over 1 litre of the catalytic material maintained
at a temperature of 260° C. at a rate of about
20,000 litres per hour of the ethylene (measured
75 at normal temperature and pressure). The
or derivatives thereof which are mentioned in our
copending application Ser. No. 738,158. Instead
of petroleum ether we may use any other suit
able volatile solvent preferably a completely vola
tile organic solvent such as benzene, and instead
of sucrose as the organic constituent to provide
the carbon skeleton in the finished catalyst we
may employ, for example, glucose, fructose,
molasses, starch, gelatine, pectin, and higher al~
cohols such as glycerol and mannitol which are
mentioned in our copending application Ser. No.
7707,416.
The organic constituent employed to
form the carbon skeleton need not be capable of 70
forming a solution or even a colloidal solution
provided it is capable of giving the desired car
bonaceous structure under the conditions of
preparation of the catalyst;'for example, pro
teins such as casein insoluble in water may be 75
3.
9,110,881
used or cellulosic material or cellulose derivatives . copper, iron, manganese, cobalt, barium, calcium,
strontium, magnesium, with an excess of phos
such-‘as cellulose esters or ethers.
phoric acid beyond. that required to form the
What we claim is:
orthophosphate 01' said element or elements,
1. A process of manufacturing catalytic ma
terial in solid pieces capable of remaining me
chanically stable when used for the vapor phase
hydration of ole?nes by means of steam under
pressure, comprising preparing a mouldable mix
ture of a metallic acid phosphate, a binder, a
10 carbonizable constituent, and a quantity 01’ water
equal to not less than about 2 per cent. or the dry
weight of the catalytic material, compacting the
material into solid pieces, and heating them sui
?ciently to produce a mechanically stabilizing
15 carbonaceous skeleton throughout each piece.
2. A process of_ manufacturing catalytic ma
terial in solid pieces capable of remaining me
chanically stable when used for the vapor phase
hydration of ole?nes by means or steam under
20 pressure, comprising preparing a mouldable mix
grinding. and again heating the mass, converting
the same into a mouldable mass by admixing
therewith an emulsion of a drying oil and a solu
tion of readily carbonizing organic matter in a
quantity of water not less than about 2 per cent.
oi’ the dry weight 0! the catalytic/material, com 10
pasting the mouldable mass into ‘small solid
pieces, and heating them su?lciently to cause car
bonization throughout each piece.
6. A process of manufacturing catalytic ma
, terial in solid pieces capable of remaining me
15
chanically stable when used for the vapor phase
hydration of olefines by means oi? steam under
_ pressure, comprising heating a mixture of an acid
decomposable compound of an element taken
from the group consisting of uranium, boron, 20
copper, iron, manganese, cobalt, barium, calcium,
ture of a metallic acid phosphate, a drying oil,
a readily carbonizing organic compound, and a ' strontium, magnesium, with an excess of phos
phoric acid beyond that required to form the
' quantity of water equal to not less than about 2
per cent. of the dry weight of the catalytic ma» orthophosphate of said element or elements, 25
grinding and again heating the mass, converting
25 terial, compacting the mixture into solid pieces,
the same into a mouldable mass by admixing
and heating ‘them sufficiently to produce a me
chanically stabilizing carbon skeleton throughout therewith a drying 011, an easily carbonizing
organic material, a quantity of water equal to
each piece.
,
not less than about 2 per cent. of the dry weight
3. A process of manufacturing catalytic maof the catalytic material, and a water dispersing 30
terial in solid pieces capable 0! remaining me
agent,
compacting the mouldable mass into small
chanically stable when used for the vapor phase
hydration of olefines by means of steam under solid pieces, and heating them su?iciently to ,
cause carbonization throughouteach piece.
pressure, comprising heating a mixture of an acid
7. A process of manufacturing catalytic mate
decomposable compound of an element taken
35
from the group consisting of uranium, boron, rial in solid pieces capable of remaining mechan
copper, iron, manganese, cobalt, barium, calcium, ically stable when used for the vapor phase
hydration of ole?nes by means of steam under
strontium, magnesium, with an excess of phos
phoric acid beyond that required to form the pressure, comprising heating a mixture of an acid
ortho-phosphate of said element or elements, decomposable compound or an element taken 40
from the group consisting of uranium, borori,
40 grinding and again heating the mass, converting
the same into a mouldable mass by admixing copper, iron, manganese, cobalt, calcium, barium,
strontium, magnesium, with an excess of phos
therewith a drying oil, an easily carbonized car
phoric
acid beyond that required to form the
bonaceous material, and a. quantity of water equal
orthophosphate
of said element or elements,
to not less than about 2 per cent. of the dry
45
weight of the catalytic material, compacting the grinding and again heating the mass, converting
same into a mouldable mass by admixing
mouldable mass into small solid pieces, and heat the
ing them sumciently to cause carbonization therewith a drying oil, an easily carbonizing or
ganic material, and a quantity of water equal to
throughout each piece.
not less than about 2 per cent. of the dry weight
4. A process of manufacturing catalytic ma
of
the catalytic material, extruding the mouldable 50
terial in solid pieces capable of remaining me
mass
through ,a die, cutting the extruded mate
chanically stable when used for the vapor phase
hydration of ole?nes by means of steam under rial into fragments, and heating them su?lciently
pressure, comprising heating a mixture of an to cause carbonization throughout each frag
'
acid decomposable compound of an element taken ment.
8. A process of treating material compounded 65
from the group consisting of uranium, boron,
from a base and phosphoric acid in excess of that
copper, iron, manganese, barium, cobalt, calcium, required
to form the orthophosphate of said base
strontium, magnesium, with an excess of phos
phoric acid ‘beyond that required to tom the so as to render it mechanically stable when used
orthophosphate of said element or elements, in the vapor phase catalytic hydration of ole 60
grinding and again drying the mass, converting ?nes by means of; steam under pressure, com
the same into a mouldable mass by admixing
therewith a drying oil and adding also a disper
sion of a readily carbonizing organic compound
in a quantity of water not less than about 2 per
cent. of the dry weight 01' the catalytic material,
compacting the mouldable mass into small solid
pieces, and heating them sumciently to cause car
bonization throughout each piece.
5. A process of manufacturing catalytic mate
70 rial in solid pieces capable of remaining mechan
ically stable when used for the vapor phase
hydration of ole?nes by means of steam under
pressure, comprising heating a mixture 01' an acid
decomposable compound or an element taken
76 from the group consisting of uranium, boron,
prising reducing the material to a dry powder, ' ‘
admixing therewith drying oil to form a mould
able mass, also admixing therewith a readily
carbonizing organic material and a quantity of
water equal to at least 2 per cent. of the dry 65
weight of the catalytic material,’ moulding the
mass into small pieces, and baking the same to ef
fect carbonization throughout of the carbonizable
material.
7
9, A process of treating material compounded 70
from a base and phosphoric acid in excess of
that required to form the orthophosphate ofsaid
base so as to render it mechanically stable when
used in the vapor phase catalytic hydration of
ole?nes by means of steam under pressure, com
7:5
4
2,110,881
prising reducing the material to a dry powder,
admixing therewith drying oil to form a mould,
able mass, also admixing therewith a solution
of a water-soluble readily carbonizing organic
material in a quantity of water equal to at least
2 per cent. of the dry weight of the catalytic ma
terial, also incorporating in the mass a volatile
organic liquid as a dispersing agent for said solu
tion, moulding the mass into small pieces, and
baking the same to effect carbonization through
used in the vapor phase catalytic hydration of
ole?nes by means of steam under pressure com
prising reducing the material to a dry powder,
admixing therewith sui?cient of a dispersion of a
drying oil in a volatile organic solvent therefor to
form a mouldable mass, also admixing there
with a readily carbonizing organic material and
a quantity of water equal to at least 2 per cent. of
the dry weight of the catalytic material, mould
ing the mass into small pieces, and baking the
same to effect carbonization throughout of the
_10. A process of treating material compounded I carbonizable material.
from a base and phosphoric acid in excess of that
WALTER PHILIP JOSHUA.
required to form the orthophosphate of said
HERBERT MUGGLETON STANLEY.
out of the carbonizable material.
base so as to render it mechanically stable when
JOHN BLAIR DYMOCK.
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1i
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