United States Patent 0 ice 2,710,883

Patented June 14, 1955

2
The following examples illustrate the invention:
Example 1
2,710,883
Av 1" stainless steel reactor tube 15" long with a
SUCCINALDEHYDE MANUFACTURE centrally located thermocouple well was packed with 95
Thomas J. Mooney, Raritan Township, Middlesex County, silver discs 1" in diameter, of 20 mesh silver gauze of
N. J., assignor to E. I. du Pont de Nemours and Com 0.014" diameter wire to a depth of 3-4" and the tube
pany, Wilmington, Del., a corporation of Delaware heated to 350° C. using an electrically heated reactor
No Drawing. Application May 1, 1951, furnace. Tetrahydrofuran (1.5 g./min.) and air (2100
Serial No. 224,074 ccs./min.) were metered into a preheated vaporizer at
100° C. and the resulting mixture passed over the heated
8 Claims. (Cl. 260-601) catalyst. The reaction off-gases were condensed by wa
ter-cooled spiral condenser and three n-propyl alcohol
scrubbers cooled in a Dry Ice bath. After 150 g. of tetra
This invention relates to the production of succinalde hydrofuran was oxidized, the reaction was shut down
hyde and in particular to a novel process for the produc and the condensate and scrubber contents were analyzed
tion of succinaldehyde from tetrahydrofuran. for succinaldehyde using hydroxylamine hydrochloride
succinaldehyde is a valuable reagent for the cross method. A yield of 16.5 g. of succinaldehyde was ob
linking of cellulose, regenerated cellulose, starch and tained together with 113.9 g. of unreacted tetrahydro
other high molecular weight substances having recurring 1* furan.
hydroxyl groups. It may, for example, be utilized to Theory yield __________________________ __g__ 179.0v
increase the wet tensile strength of paper and to increase Percent conversion yield ___________________ __ 9.2
the water resistance of starch. succinaldehyde is also Percent net yield ________________________ __ 43.1
a useful chemical intermediate. '
It is an object of this invention to provide a new, ~ Example 2
useful and economical process for'the production of A l”stainless steel reactor 15" long with a centrally
succinaldehyde. Another object is to provide a practical located thermocouple well was packed with 25 discs of
process for the production of succinaldehyde from tetra copper gauze to a depth of 1-1.5" and the tube heated
hydrofuran. These and other objects will be apparent to 345-365 ° C. using an electrically heated reactor fur~
from the ensuing description of the invention. nace. Tetrahydrofuran (1.5 g./min.) and air (2100
The objects of this invention are attained by passing ccs./min.) were metered into a preheated vaporizer at
tetrahydrofuran and an oxygen-containing gas into con 100° C. and the resulting mixture passed over the heated
tact with a metallic silver or copper catalyst at a tem catalyst. The reactor off-gases were condensed by a
perature of 200° to 500° C. in the vapor phase. water-cooled spiral condenser and three n-propyl alcohol
In one mode of carrying out the invention a mixture of ; scrubbers cooled in a Dry Ice bath. After 150 g. of
tetrahydrofuran and air is passed through a preheater tetrahydrofuran was oxidized, the reaction was shut down
at a temperature suliiciently high to vaporize the tetra- ‘ and the condensate and scrubber contents analyzed for
hydrofuran and the mixture is passed from the preheater succinaldehyde using hydroxylamine hydrochloride
into contact with a metallic silver or copper catalyst main method. A yield of 16.4 g. of succinaldehyde together
tained at a temperature of 200° to 500° C. The gaseous ., with 123.6 g. of unreacted tetrahydrofuran was obtained.
products are condensed and succinaldehyde is isolated
by vacuum distillation. Unreacted tetrahydrofuran may Theory yield (succinaldehyde) __________ __g__ 179.0
be recycled. I
Percent conversion yield __________________ __ 9.2
Percent net yield _________________________ __ 52.0
It is essential that the reaction temperature be main
tained at 200° to 500° C. At temperature below 200° C. - Example 3
or above 500° C. appreciable amounts of succinaldehyde A 1" stainless steel reactor tube with the centrally
are not formed. Better results are obtained within the located thermocouple well was charged with 15 cos. of
range 300 to 400° C. and it is preferred to operate at silver crystals (held on 20 mesh screen) to a depth of
temperatures of 340° to 360° C. for optimum results. 2% inches and heated to 330—360° C. using an electri
Although both silver and copper catalysts are satis .70 cally heated reactor furnace. Tetrahydrofuran (1.5
factory in the operation of this invention, it is usually g./min.) and air (2100 cos/min.) were metered into
preferred to utilize silver as the catalyst since it has been the preheated vaporizer at 100° C. and the resulting
found that under the conditions of the reaction copper mixture passed over the heated catalyst bed. The reactor
is rather easily oxidized to copper oxides and the latter off-gases were condensed by a water-cooled spiral con
promote uncontrollable exothermic oxidation of the tet a denser and three Dry Ice-cooled n-propyl alcohol scrub
rahydrofuran to carbon oxides and water thus decreasing bers. After 150 g. of tetrahydrofuran was oxidized the
the efficiency of operation. The metallic catalyst may reaction was stopped and condensate and scrubbers an
be used in any desired form either alone or on inert sup alysed for succinaldehyde by the hydroxylamine hydro
ports such as silica, alumina or other well-known ma chloride method. A yield of 11.6 g. of succinaldehyde
terials. Good results have been obtained, for example, was obtained together with 114 g. of unreacted tetrahy
with silver crystals, silver gauze, silver-on-alumina, cop drofuran.
per-on-silica and copper gauze. Theory yield __________________________ __g__ 179.0
Oxygen or gas mixtures containing oxygen are suit Percent conversion yield ___________________ __ 6.5
able for carrying out the process. It is preferred to Percent net yield _________________________ -_ 27.0
utilize air as the oxygen-containing gas for economic Example 4
reasons.
The proportion of oxygen to tetrahydrofuran is not The 1" stainless steel reactor tube with the centrally
located thermocouple well was charged with 15 cos. of
critical and may be varied over wide limits with suc
silver-plated “boileezers” (precipitated silver an A1203)
cessful results. In general it is desirable that the vapor approximately 4-6 mm. in diameter to a depth of 2%
mixture passing into contact with the catalyst contain inches and heated to 315-325” C. using an electrically
about 2 to 26% by volume of tetrahydrofuran. heated reactor furnace. Tetrahydrofuran (0.75 g./min.)
 2,710,883
3 4
and air (1040 g./min.) were metered into a vaporizer at I claim:
100° C. and the resulting mixture passed over the heated 1. The process for the production of succinaldehyde
catalyst bed until 150 g. of tetrahydrofuran was vapor which comprises passing tetrahydrofuran and an oxygen
ized. The reactor off-gases were condensed by a water containing gas into contact with a catalyst from the group
cooled spiral condenser and three Dry-Ice-cooled n-propyl consisting of metallic silver and copper at a temperature
alcohol scrubbers and analyzed for succinaldehyde. A of 200° to 500° C. in the vapor phase.
yield of 1.6 g. of succinaldehyde was obtained together 2. The process of claim 1 wherein the oxygen-contain
with 105.4 g. of water and unreacted tetrahydrofuran. ing gas is air.
3. The process of claim 1 wherein the temperature is
Example 5 10 340° to 360° C.
A copper on silica catalyst prepared by coagulating 4. The process for the production of succinaldehyde
equal portions of copper dust and silica in a 30% colloidal which comprises passing tetrahydrofuran and an oxygen
silica solution, was baked to dryness at 120° C. and containing gas into contact with a metallic silver catalyst
screened to #6 mesh size. The 1" stainless steel reactor at a temperature of 200° to 500° C. in the vapor phase.
was charged with 15 ccs. of this catalyst and heated to 5. The process for the production of succinaldehyde
350° C. using an electrically heated reactor furnace. which comprises passing tetrahydrofuran and air into
Tetrahydrofuran (1.5 g./min.) and air (2000 cos/min.) contact with a metallic silver catalyst at a temperature of
were metered into a vaporizer at 100° C. and the mixture 340° to 360° C. in the vapor phase.
passed over the heated catalyst bed until 150 g. of tetra 6. The process which comprises contacting a vapor
hydrofuran was oxidized. The reactor gases were con- V phase mixture of tetrahydrofuran and an oxygen-con
densed by a water-cooled spiral condenser and a series taining gas with a catalyst of the group consisting of
of three n-propyl alcohol scrubbers cooled in a Dry Ice metallic copper and silver at a temperature of 200°-500°
bath and anlyzed for succinaldehyde using hydroxylamine C. and subsequently recovering succinaldehyde from the
hydrochloride. A yield of 2.0 g. of succinaldehyde was resultant mixed gases.
obtained together with 88 g. of water and unreacted tetra 7. The process which comprises contacting a vapor
hydrofuran. phase mixture of tetrahydrofuran and air with a metallic
Example 6 copper catalyst at a temperature of about 340°—360° C.
and subsequently condensing succinaldehyde from the re
The 1" stainless steel reactor tube was charged to a
depth of 2-3" with bronze window screen clippings and sultantmixed gases.
8. The process which comprises contacting a vapor
heated to 350° C. using an electrically heated reactor l phase mixture of tetrahydrofuran and air with a metallic
furnace. Tetrahydrofuran (1.5 g./min.) and air (2100 silver catalyst at a temperature of about 340°~360° C.
g./min.) were metered into a vaporizer at 100° C. and and subsequently condensing succinaldehyde from the
the mixture passed over the heated catalyst bed until
150 g. of tetrahydrofuran was oxidized. The reactor
resultant mixed gases.
gases were condensed by a water-cooled spiral condenser ‘ References Cited in the ?le of this patent
and a series of three n-propyl alcohol scrubbers cooled
in a Dry Ice bath and analyzed for succinaldehyde by UNITED STATES PATENTS
hydroxylamine hydrochloride procedure. A yield of 2,075,100 Dreyfus ____________ __ Mar. 30, 1937
5.4 g. of succinaldehyde was obtained together with 135.9 2,246,569 Brown ______________ __ June 24, 1941
g. of unreacted tetrahydrofuran and water. FOREIGN PATENTS
Theory yield (succinaldehyde) __________ __g__ 179.0 699,945 Germany ____________ __ Dec. 10, 1940
Percent conversion yield __________________ __ 3.0 608,539 Great Britain ________ __ Sept. 16, 1948
The succinaldehyde product was identi?ed by forma OTHER REFERENCES
tion of succinaldoxime which melted at 169° to 171° C.
The process of this invention provides a simple and Ind. and Eng. Chemistry (February 1948), vol. 40,
practical method for the production of succinaldehyde, a No. 2 (pp. 217-218).
valuable reagent for cross-linking cellulose and other ma
terials and a useful chemical intermediate.