Agglomerates of spheroidal masses of malachite crystals are prepared so that they contain

silicic acid. These agglomerates can be used to prepare a copper-acetylide complex, which in
turn can be used as a catalyst for the preparation of 1,4-butynediol from acetylene and
formaldehyde.Claim:I claim:

1. The process of preparing 1,4-butynediol by the reaction of acetylene and formaldehyde,
using as the catalyst a complex produced by subjecting agglomerates of spheroidal masses
ofmalachite crystals, which crystals contain 1-7% by weight of bismuth oxycarbonate and
0.5-3.5% by weight (calculated as SiO.sub.2) of silicic acid, to the action of acetylene and
formaldehyde.

2. The process of preparing 1,4-butynediol by the reaction of acetylene and formaldehyde,
using as the catalyst a complex produced by subjecting agglomerates like those described in
claim 1, having an average longest dimension of about 15microns, with at least about 95% of
the agglomerates having a longest dimension of 14-18 microns, and the spheroidal masses of
malachite crystals having an average longest dimension of about 5 microns, with at least
about 95% of the masses having alongest dimension of 3-8 microns, to the action of acetylene
and formaldehyde.Description:TECHNICAL FIELD

This invention relates to a new form of basic copper carbonate (malachite). It is more
particularly directed to agglomerates of spheroidal masses of malachite crystals, to a method
for preparing them, to copper acetylide catalysts prepared fromthe crystals, and to the use of
the catalysts in the preparation of 1,4-butynediol from acetylene and formaldehyde.

BACKGROUND AND SUMMARY OF THE INVENTION

Large amounts of 1,4-butynediol are produced every year, chiefly as an intermediate in the
preparation of tetrahydrofuran. In that preparation, the butynediol is hydrogenated to 1,4-
butanediol, which is then dehydrated and cyclized totetrahydrofuran.

It has been a common practice in years past to make 1,4-butynediol from acetylene and
formaldehyde, using as a catalyst a copper acetylide complex. This is shown in my U.S. Pat.
No. 4,110,249, in which I describe a catalyst made from malachitein the form of spheroidal
masses of crystals which contain bismuth oxy-compounds to supress cuprene formation.

Such a catalyst is quite satisfactory, but I have found that its resistance to degradation by
attrition can be improved if the malachite from which it is prepared also contains 0.5-3.5% by
weight, of silicic acid. I have also found that thesilicic acid gives the catalyst higher activity,
and that this higher activity is sustained for a longer period than with my earlier catalyst.

DETAILED DESCRIPTION OF THE INVENTION

The malachite of the invention can be made by a three-stage process. In the first stage, an
amorphous gel-like hydrated copper carbonate is prepared by bringing together, with
agitation, in aqueous solution, a cupric salt, a bismuth salt, analkali metal carbonate or
bicarbonate, and silicic acid. In this first stage, only 30-60%, by volume, of the total amount
of the cupric salt, the bismuth salt and the silicic acid needed are used, as precalculated before
the preparative process isbegun.

Although any form of silicic acid can be used, I have found that a much more effective
catalyst is obtained if the silicic acid is preformed by mixing together about 100 parts by
volume of water, about 10 parts by weight of sodium silicate andabout 10 parts by volume of
nitric acid, with stirring. This gives a colloidal suspension of silicic acid, which can be used
directly in preparing the malachite.

Any water soluble cupric salt can be used. Illustrative are the nitrate, the chloride and the
sulfate. Cupric nitrate is preferred.

Similarly, any water soluble bismuth salt can be used. Illustrative are the nitrate, the
oxycarbonate, the citrate, the sulfate and the phosphate. The nitrate is preferred.

Of the alkali metal carbonates and bicarbonates which can be used, sodium carbonate and
sodium bicarbonate are preferred.

Each salt solution is prepared so that it contains as much salt as possible without it
crystallizing from solution on standing or during use.

The copper salt solution, the bismuth salt solution and the silicic acid solution are then
brought together in such proportions that the resulting mixture contains 1-10%, by weight of
its copper content of bismuth salt, and 0.1-2% by weight ofsilicic acid. The pH of the mixture
is maintained at about 5.5-7.5, preferably 6.5-7.0, by the addition of appropriate amounts of
the alkali metal carbonate or bicarbonate solution.

The solutions can be brought together in any order, generally over a period of 10-30 minutes,
with stirring. In a preferred embodiment, a solution of the copper salt, the bismuth salt and
the silicic acid is prepared and this is fed to a smallamount of water, simultaneously with a
solution of the alkali metal carbonate or bicarbonate.

The resulting mixture of salts is held at a temperature of just slightly above the freezing point
of the mixture to about 55.degree. C., preferably 45.degree.-55.degree. C., with stirring. An
amorphous mass of gel-like hydrated coppercarbonate forms immediately.

In the second stage, the product of the first stage is held at a temperature of 45.degree.-
55.degree. C., without stirring or agitation of any kind. Carbon dioxide evolves and masses of
malachite crystals form. Crystal formation is ordinarilycomplete in 10-30 minutes.

In the third stage, this medium containing masses of malachite crystals is stirred and held at a
temperature of 45.degree.-55.degree. C. while the remainders of the solutions of cupric salt,
bismuth salt and silicic acid to be used are added, atabout the same rate as that used in the
first stage. As in the first stage, the pH of the reaction mass is maintained in the range 5.5-7.5,
preferably 6.5-7.0, by addition of the alkali metal carbonate or bicarbonate solution. It is in
this stage thatthe spheroidal masses of malachite crystals agglomerate to form the malachite
of the invention.

After this third stage is complete, ordinarily a matter of 10-60 minutes, the malachite is
filtered from the reaction medium and washed free of residual salts with water.

The resulting product, agglomerates of spheroidal masses of malachite crystals, contains 0.5-
3.5% by weight (calculated as SiO.sub.2) of silicic acid, preferably 0.5-1%. This is uniformly
distributed throughout the crystals, although with higherconcentrations, a bit more tends to
appear at the surfaces of the crystals.

The crystals also contain 1-7%, by weight, of uniformly distributed bismuth oxy-compound.

Although the benefits of my invention are largely independent of the dimensions of the
spheroidal masses of malachite crystals and the agglomerates of these masses, I have found
that a catalyst much easier to filter from the reaction mass and ofa much more uniform
composition can be obtained if the malachite from which it is prepared is composed of
agglomerates having an average longest dimension of about 15 microns, with at least about
95% having a longest dimension of about 14-18 microns, andif the spheroidal masses of
crystals have an average longest dimension of about 5 microns, with at least about 95% of the
masses having a longest dimension of 3-8 microns, all as determined by a Coulter Counter, or
as measured optically against astandard.

This preferred malachite can be prepared according to the method just described if, in the first
stage, the solutions are brought together in a small amount of water containing a small
amount, e.g., about 0.2-2%, by weight, of a pre-formed seedof the malachite of the invention.
This seed can be added directly to the water, or it can be present as residue from a previous
preparation.

The malachite produced in this way can be converted to a copper-acetylide complex by
preparing a slurry of it in water and then subjecting this slurry to the action of acetylene and
formaldehyde. This procedure is described in more detail inKirchner U.S. Pat. No. 3,650,985,
beginning in column 5. The portion of the Kirchner patent which describes this procedure is
incorporated into this specificaton by reference.

This copper-acetylide complex can be used directly as a catalyst for the reaction of acetylene
and formaldehyde to produce 1,4-butynediol. The complex is used in the customary way and
in the usual amounts, and no special techniques orprecautions are needed. Details for this use
can be found in the aforementioned Kirchner patent.

EXAMPLES

Those skilled in this art will be able to practice this invention more easily after referring to
the following illustrative examples.

These artisans will no doubt be able to compose numerous variations on the themes
disclosed, such as changing the amounts of components used slightly but insignificantly from
those shown, adding innocuous substances, or substituting equivalent ornearly equivalent
components for those shown. I consider all these variations to be part of my inventive
concept.

In the examples, all parts are by weight.

EXAMPLE 1--PREPARATION OF MALACHITE

(a) In 900 parts of water were dissolved

Cu(NO.sub.3).sub.2 H.sub.2 O: 980 parts

Bi(NO.sub.3).sub.3 5H.sub.2 O: 35 parts

HNO.sub.3 (concentrated): 90 parts

(b) A mixture was prepared of

Water: 100 parts

HNO.sub.3 (concentrated): 10 parts

Sodium silicate: 10 parts

(c) The mixture of (b) was added to the solution of (a), with stirring.

(d) 675 parts of anhydrous Na.sub.2 CO.sub.3 were dissolved in 3300 parts of water.

(e) A reaction vessel was charged with 3300 parts of water containing 0.2 parts of malachite
crystals prepared in a previous run.

This charge was heated to and held at 45.degree. C., with stirring, while half of the solution
of (c) was fed in over a 15 minute period. Enough of the solution of (d) was concurrently fed
into the charge to hold the pH at 6.5-7.0.

When the feed was complete, stirring was stopped and the temperature of the reaction mass
held at 45.degree. C. for 20 minutes. A blue-green gel formed which gradually changed to
masses of green malachite crystals.

Stirring was then resumed, and the remainder of solution (c) was added to the reaction mass
over a 15 minute period, while the temperature of the mass was held at about 47.degree. C.
and the pH held at 6.5-7.0 with solution (d).

The agglomerates which formed had an average diameter of 15-17 microns, and were
composed of spherical masses of malachite crystals, the masses having an average diameter
of about 6 microns. The crystals contained 0.67%, by weight, of silicicacid.

These agglomerates were filtered from the solution, washed with water, and dried.

EXAMPLE 2--PREPARATION OF COPPER--ACETYLIDE COMPLEX

A reaction vessel was charged with 600 parts of a 47% solution of formaldehyde in water
(having a pH of 7.0), and 100 parts of the malachite prepared in Example 1.

An acetylene nitrogen mixture was sparged into the vessel at a rate which kept the solids in
suspension and gave a pressure of 5 psig. The temperature of the reaction mass was held at
65.degree.-75.degree. C. and its pH was held at 5.0-6.5 withsaturated sodium carbonate
solution.

The effluent gas stream, composed of carbon dioxide, nitrogen and acetylene, was bifurcated.
One portion was vented to the atmosphere and the other recycled to the reactor. The vent rate
and acetylene feed rate into the reactor were controlledto keep the acetylene concentration in
the reactor in the range 1-5% at all times.

After about 6 hours, CO.sub.2 evolution declined. The vent rate and the acetylene feed were
then increased so that acetylene replaced the vented CO.sub.2, until CO.sub.2 evolution
stopped.

Pressure was then released, the product cooled and removed from the reactor.

EXAMPLE 3--PREPARATION OF 1,4-BUTYNEDIOL

A reaction vessel was charged with the catalyst prepared in Example 2 and 600 parts of
formaldehyde (45% solution in water). A stream of acetylene was then continuously passed
through the vessel at a rate which kept the solids suspended andprovided an acetylene
pressure of about 5 psig. The temperature of the reaction mass was held at about 90.degree.
C., and its pH at about 6 with a saturated solution of sodium bicarbonate.

The reaction was continued for two hours, at which point about 5%, by weight, of the original
formaldehyde charge remained.
* * * * *
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DESCRIPTION
[0001]

[0002]
The present invention relates to an improved process for the manufacturing of 1,4-butynediol,
and to the related catalyst. 1,4-butynediol. has. been and is today used as an intermediate for
the production of butadiene: 1,4-buty nediol is hydrogenated to 1,4-butanediol, from which
buLa diene is obtained through bilateral dehydration.
[0003]
Furthermore 1, 4-butanediol too has recently found an increasing use for the production of
saturated polyester resins (especially PBT), of expanded and polymeric polyuretha ne resins
and in the production of tetrahydrofuran by mono-dehidration.
[0004]
The typical reaction schema for the production of 1,4-buLy
nediol
is illustrated by the following
reactions:


Such a synthesis was disclosed for the first time, from the industrial point of view, in the USP
2,232,867 to Reppe et al; more particularly, as the catalyst, monovalent copper supported
onto an inoi-ganic polymer (SiO
2
)
n
was indicated, the catalyst being prepared by impregnation
and subsequent calcination. According to the preferred modification of this process, besides
the monovalent. copper, the catalyst was al so impregnated with a small percentage of
bismuth, having the purpose of enhancing the selectivity of the catalyst and inhibiting the
polymerization of acetylene to cuprene.
[0005]
This is a very important feature, since the catalyst becomes coated with cuprene, thus
inhibiting the catalytic fun-cLion and clogging the catalyst bed with the self-evident problems.
[0006]
Thereafter several other supports for the active metal have been proposed, such as carbon,
pumice, magnesuim sili cates, aluminium, or inorganic mixtures of magnesium and alu
aluminium salts and/or oxides.
[0007]
It is to be noted that according to the process disclosed in the above numbered U.S. patent
(Reppe et, al) and to the industrial processes as carried out to date the reaction was effected
under pressures of about 5 to 7 atmospheres and at a temperature of between 90 and 95C;
the fact should not be neglected that, under the above pressures, parLicu-lar cautions are to
be adopted, in order to prevent acetylene from undergoing explosive decomposition.
[0008]
Moreover, accordingto the industrial process as used to date, by operating under the above
indicated conditions and with a catalyst containing at least 12% copper and at least 6%
bismuth, production rates were obtained (as reported in the literature) of about 1 kg 1,4
butynediol/1kg catalyst/ /24 hours operation.
[0009]
The main purpose of the present invention is that of previ ding a process for the production of
1,4-butynediol accor ding to which:
o 1- the activity and the selectivity of the catalyst, thus increasing the production rate,
and the reaction can be carried out under pressure and temperature conditions
definitely lower than the dangerous limits as regards the explosive decomposition of
acetylene;
o 2- the formation of cuprene is essentially eliminated, whe reby the catalytic bed and
the catalyst activity are esse ntially safeguarded.
[0010]
It has been now found, which is the subject of the present. invention, that these purposes are
essentially achieved by means of a process for the preparation of 1,4-butynediol, wherein
acetylene is reacted with formaldehyde in the presence of a metal catalyst, particulary and
preferably Cop per supported onto an inert support, characterized in that a vinylpyridine
polymer is used as the catalyst support said polymer being complexed with the catalytic
metal. According to the preferred embodiment, said vinylpyridine polymer is a copolymer of
the vinylpyridine with a comono mer selected among vinylaromatic and vinylaliphatic
monomers. According to an alternative embodiment of the present invention said support of
the metal comprises a vinylpyry dine homopolymer, said support beirg complexed with the
said catalytic metal and being convenienthly swelled with a suitable solvent before and/or
during the reaction.
[0011]
In both the embodiments of the invention the above reaction is effected at a temperature of
between 70 and 100C and a
L
a pressure not higher than 1.5 atmospheres, higher pres sures
being however possible under the due cautions.
[0012]
Taking now in a more specific account the several parameter of the process of the present
invention, it is clear that the relevant and highly surprising advantages of the invention are a
consequence of the catalyst used for the reaction and particularly of the support complexed
with the catalytic metal. It is necessary to point out that polymers of 4-vinylpyridine were
already proposed in the past as ca talyst support (E.M. Cermia, M. Graziani, J. Applied
Polymer Science, Vol. 13 pag. 2742 (1974), "Alcohol Carbonyla tion, and Ind. Eng. Chem.
Prod. Res. Dev. Vol. 17 No. 2 (1978) pag. 128, "0xidative Coupling of Diphenylmethanimine
Catalized by copper Loaded Copolymers of 4-vinylpiridine and DVB)".
[0013]
However, in all these cases, the possibility pf employing these catalyst supports in the
reaction of the Reppe process has never been even ventilated.
[0014]
Furthermore neither the high increase of production rate, as noted in the process of the
present envention (which shall ! be confirmed by the following examples), nor the essential
elimination or cuprene formations was completely unforesa-ble.
[0015]
As the plymers namely homopolymers and copolymers) of 4-vinylpyridine to be used in the
present invention, Llieie aru nmant, those having a molecular weight of at least 5,000 and
preferably of between 30,000 and 50,000.
[0016]
A possible explanation although without limiting meaning, of the operating mechanism of the
catalyst used in the process of the present invention is that the catalytic metal is complexed
by the polymeric molecules, containing electron donor groups, these groups in the case of the
copolymers being separated by non-donor groups.
[0017]
Since these electron donor groups form somewhat like active sites, responsible of the
complexation with the catalytic metal, by varying the swelling (in the case of homopolymer) or
the number of comonomer molecules separating electron do nor groups, it is possible to
space from each other the atoms of the catalytic metal, the catalytic action promoting the
cuprene formation being thus made statistically unlikely.
[0018]
At the same time due to the macroporous or swelled nature of the support polymer, the
surface of the support available for the catalytic metal is increased, whereby the activity and
selectivity of the catalyst are gretly improved, since there is made easier and/or more
probable the access of rea ctans to atoms of the catalytic metal which otherwise would
remain unused.
[0019]
In the case of the homopolymers of vinylpyridine the solvent used for the swelling of the
polymer support is, as a rule, inert. with respect to the components of the reaction mixture,
particularly a polar solvent; preferably this solvent is selected among aliphatic, alicyclic and
cyclic alcohols.

[0020]
On the contrary, according to the process of the present in- vention, if account is also taken of
the reaction temperatures, si.nce the greater is the temperature the higher is the reaction
absolute pressure, the maximum partial pressure of the acetylene, fed at a relative pressure
of 1.5 atmospheres achieves in the reaction vessel a relative pressure of 520 mmHgand,
moreover, in a condition of saturation with steam . For a comparison with the dangerous
levels indicated in the literature, see S. A. Miller, "Acetylene", E. Bems Edit. Ltd London 1945,
chap. 0 pag. 476.
[0021]
A further advantage connected with the use of relatively low acetylene pressures is that is
concurs to reduce the formation of acetylene polymers, namely cuprenes, the importance of
which as regards the process and particularly as regards the useful life of the catalyst has
been discussed above.
[0022]
Of course, the use of higher pressures of acetylene still comes within the scope of the present
invention. The following examples are given only to illustrate the invention, and should not be
construed as limiting the sco--pe of the invention.
[0023]
The' homopolymer and the copolymer, cross-linked with divinylbenzene , were supplied by
CRODA Synthetic Chemicals Ldt.
[0024]
The gas-chromatographic analyses were carried out by means of a Perkin-Elmer Sigma 3
chromatographic apparatus, having
a
Sigma 10 comnuter, by using a 1m long glass
columm,pac
ked
with Carbowax 3 % on Cromosorb, of the diameter of 3 mm.
[0025]
The analyses of the copper present onto the catalyst were carried out according to the
iodometric method (ASTM 34-68) and those relating to the formaldehyde according to the Na
2 SO
3
method. 3
[0026]
The preparation of the catalytic complexes was effected by using the normal techniques, well
known in the art.
Example 1
[0027]
In an oscillating steel autoclave, having an acetylene entrance cock, a thermometric well for
the temperature control a volume of 320 .cu.cm. and heated by means of an electrical
resistance, there are charged 4.8 g of the complex containing 20% Cu coordinated with the
ligands contained in the polymer matrix of the 4-vinylpyridine homopolymer, and 180 mls of a
30% HCHO solution (486 g of HCHO) in isobutanol Oxygen is eliminated from the reaction
environment according Lo the normal technique of several purging passes of pure nitrogen.
[0028]
Before starting the heating and the stirring a vacuwn of about 0,1 ata is established in the
autoclave.
[0029]
When the temperature has attained 120C, C
2
H
2
is fed up to 2.5 absolute atmospheres. The
absolute pressurecf C
2
H
2
in this case is 989 mm Hg and thus lower than whatever dan
gerous limit.
[0030]
After 4 hours, needed for the catalyst formation, the mo nitoring of the production rate is
commenced by gas-chroma tographic analysis of small samples taken each hour for Llit-
subsequent six hours.
[0031]

[0032]
the following examples were carried out in glass autoclaves, having a capacity of 500 cu,cm.
an acetylene entrance cock and a further tap connected to an equipment for establishing a
vacuum within the autoclave
[0033]
The latter was heated by a thermostatic oil oath at the temperature of 95C, and the internal
temperature was determined by means of thermocouple placed in a thermowell. The reaction
mixture was stirred by means of a magnetic stirrer.
Example 2
[0034]
The autoclave is charged with 200 mls of 36% HCHO (79g) water solution and with 10 g of
the Cu complex (Cu 4.1% ), the ligands being part of a polimeric matrix comprising 4--
vinylpiridine (60% by weight) and divinlbenzene (40%). Acetylene is continously fed through a
pipe dipped within the solution.
[0035]
The partial pressure of acetylene is 515 mm lig and thus de finitely less than the dangerous
threshould.
[0036]
After the 4 hours time necessary for the catalyst formation, the monitoring of the production
rate is commenced, through the gas-chromatographic examination of small samples taken
every hour. The results indicated a production rate of pro pargyl alcohol of 0,024 g/1g catalyst
x 1h and of 1,4-buty nediol of 0.06 g/lg catalyst x lh.
Example 3
[0037]
Under the same temperature and pressures conditions (90C of internal temperature and '2,5
absolut.e atmospheres of C
1
H
2
feed pressure)) the reaction is carried out with 10 g of a
complex containing 3% Cu coordinated with the ligand groups of a polimeric matrix
comprising 4-vinylpyri-

[0038]
under conditions of steady operation there are obtained O,017 g 1g catalyst X I h of propagyl
alcohol and 0,23 g/1g catalyst 1 h of 1,4-butynediol .
[0039]
In the preceding exmples reference has been made to the catalyse of metal copper supported
on a polimeric matrix, buL the same polimeric support is suitable as well for any other metal
adapted to form with acetylene, under the spe cific reaction conditions, the corresponding
acetylides, such as for example Ni, Hg, Au; Pd and the like.
PATENT CITATIONS
Cited
Patent
Filing
date
Publication
date
Applicant Title
DE2429269B2 * 19 Jun 1974 31 Aug 1978
Sumitomo Chemical
Co., Ltd., Osaka
(Japan)
Title not
available