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Patented June 29, 1943 2,322,915

UNITED STATES PATENT OFFICE 2,322,915


MANUFACTURE OF OXALC; ACD
Maxwell J. Brooks, Beverly Hills, Calif., assignor
to General Chemical Company, New York,
N. Y., a corporation of New York
No Drawing. Application September 27, 1941,
Serial No. 412,600
9 Claims. (C. 260-528)
This invention relates to the manufacture of found that by operating in this manner optimum
Oxalic acid from carbohydrates, and more par yields of high-grade oxalic acid are obtained.
ticularly to the manufacture of oxalic acid by The Oxalic acid produced in accordance with my
catalytic oxidation of carbohydrates with nitric invention may be recovered by permitting the
acid. oxidation mass to cool, whereby the oxalic acid
It is known that Oxalic acid may be prepared crystallizes therefrom, or may be removed from
by the Oxidation of carbohydrates such as glu the reaction mass in any other desirable manner.
cose, sucrose, starch, dextrin, cellulose and the In every case, it will be found that the yields
like with nitric acid. For example, United States of oxalic acid are substantially greater than
Patent 2,057,119, issued to Simpson October 13, O yields obtained when vanadium alone is employed
1936, describes a method for manufacturing as the catalytic agent. My invention, therefore,
Oxalic acid involving oxidizing a carbohydrate, provides a method for producing increased quan
such as glucose, with nitric acid in the presence tities of Oxalic acid by oxidation of carbohydrates
of Sulfuric acid at a temperature between about without substantially increasing the cost of pro
150' and 160° F., while maintaining the carbo 6 duction.
hydrate in excess of the nitric acid during the The oxidation of the carbohydrates with nitric
Oxidation; the patent states that vanadium acid in accordance with this invention may be
pentoxide may be added to the mass to catalyze carried out in any suitable manner. The carbo
the oxidation. While this method of preparing hydrate employed is preferably a monosaccharose
Oxalic acid has been found to yield a high-grade 20 Such as glucose, fructose and the like, although
product in a simple and efficient manner, the other carbohydrates such as sucrose, starch, dex
yields of Oxalic acid are not as large as might trin, etc., may also be employed; however, when
be desired. However, to my knowledge no suc employing carbohydrates other than the mono
cessful method for obtaining higher yields of 25 Saccharoses it is preferable to hydrolyse them with
acid to form monosaccharoses before subjecting
Oxalic acid by catalytic oxidation of carbohy
drates with nitric acid has been developed prior them to oxidation with nitric acid. The nitric
to my invention, acid employed in accordance with this invention
It is an object of this invention to provide a may be of any suitable concentration, varying, for
novel Catalyst for use in the production of Oxalic example, from about 60% to 95% HNO3. As
acid by oxidation of carbohydrates with nitric 30 hereinabove pointed out, oxidation with nitric
acid. acid is preferably carried out in the presence of
Sulfuric
It is a more specific object of this invention acid in the acid; the concentration of the sulfuric
to provide an improved method for preparing oxidation mass may vary somewhat,
Oxalic acid by catalytically oxidizing carbohy but it is preferable to adjust the sulfuric acid ,
drates with nitric acid in the presence of sulfuric 35 concentration so that the mother liquor, after
acid. w removal of the oxalic acid product from the
I have made the surprising discovery that the oxidation mass, contains about 50% sulfuric acid,
yields of Oxalic acid obtainable by oxidizing car since if the sulfuric acid concentration is per
bohydrates with nitric acid in the presence of a mitted to fall materially below this value, the
vanadium catalyst may be substantially improved 40. Oxalic acid tends to oxidize to carbon dioxide,
by conducting the oxidation in the presence of thus reducing the yield of product. The vana
controlled amounts of iron so that the oxidation dium-iron catalyst may be formed by dissolving
mass contains at least about 0.1%, preferably be Suitable vanadium and iron compounds in the
tween about 0.39% and about 0.8%, ferric iron. acid reaction mixture; the vanadium is prefer
ably derived from vanadium pentoxide, whereas
A preferred embodiment of my invention involves 45 iron
catalytically oxidizing a carbohydrate such as may be incorporated in the reaction mix
glucose with nitric acid in the presence of Sul ture by dissolving iron, iron oxide or other solu
furic acid and a vanadium-iron catalyst at a ble iron compounds in the acid medium.
temperature between about 150° and about 165° In the practice of a preferred embodiment of
F. while maintaining in the reaction mass an 50 this invention, which may be carried out con
amount of carbohydrate in excess of the amount tinuously or batchwise, oxalic acid mother
required to react with the nitric acid, the cata liquor from a previous operation, from which
lyst being employed in an amount sufficient to Oxalic acid crystals have been removed and
maintain in the oxidation mass between about which contains about 50% sulfuric acid, is run
0.39% and about 0.8% ferric iron, since I have into a reaction vessel. This liquor, in accord
2 2,322,915
ance with my invention, should contain dis Oxalic acid product may be recovered as here
solved therein at least about 0.1%, and pref inabove described.
erably between about 0.39% and about 0.8%, The following examples are illustrative of my
ferric iron and between about 0.001% and about invention. Amounts are given in parts by
0.05% vanadium (expressed as WOs); if neces weight.
sary, sufficient iron and vanadium, in the form Eacample 1.-Raw starch (containing 85.45%
of vanadium pentoxide, may be dissolved in the starch) was hydrolyzed by gradually dissolving
mother liquor to adjust the catalyst content the starch in an 11% oxalic acid solution at a
thereof to within these preferred ranges. The temperature between about 167 and 176' F. in
maximum amount of iron present in the oxida O the proportion of 42.72 parts of starch (100%)
tion mass may vary, but an amount of iron in per 57.28 parts of solution, and refluxing the
excess of that required to produce a saturated solution thus formed for six hours; the starch
solution of iron salts in the Oxidation mass at was thereby hydrolyzed, chiefly to glucose. 800
room temperature (about 70 F.) is undesir parts of this hydrolyzed starch solution were
able. A mixed acid solution containing nitric 5 mixed with 2696 parts of oxalic acid mother
acid and sulfuric acid is also prepared, a further liquor recovered from a previous operation and
quantity of the mother liquor serving as the containing 46.77% sulfuric acid, 5.46% oxalic
source of sulfuric acid; sulfuric acid from an acid, 0.64% ferric iron, and 0.00i 87% vanadium
external source may also be added to the mix (expressed as W2O5). The solution was then
ture to replace any sulfuric acid lost during 20 heated to 160° F. and 905 parts of 95% nitric
the previous oxidation. The mother liquor in acid were added thereto over a period of three
the reaction vessel may then be heated to 150 hours. The naSS Was maintained at 60' . for
to 165° F.; an aqueous glucose Solution con an additional two hours, during which time
taining desirably about 60% glucose, diluted with 59.5 parts of 95% nitric acid were added to
a portion of the mother liquor to increase its 25 complete the oxidation; it was then cooled to
fluidity, and the mixed acids may then be intro 90° F. and the oxalic acid crystals which formed
duced into the reaction vessel with agitation, were separated from the mother liquor. The
the temperature being maintained between yield of oxalic acid amount to 1.653 parts of acid
about 150° and about 165° F. The rates of addi per part of starch.
tion of the glucose and mixed acid solutions, and 30 Eacample 2.-800 parts of hydrolyzed starch
the concentrations of these solutions, are regu prepared as described in Example were mixed
lated so that an excess of glucose is maintained with 2280 parts of Oxalic acid mother liquor con
in the reaction mass during the course of and taining 55.36% sulfuric acid, 4.23% oxalic acid,
up to completion of the oxidation. Nitrogen 0.39% ferric iron and 0.005% vanadium (ex
oxide vapors which are evolved may be col 35 pressed as W2O5). The solution was then heated
lected in an absorber and the acid thus recov to 160° F., and 1318 parts of 65% nitric acid
ered used as desired. When the Oxidation has gradually added thereto while maintaining the
proceeded to completion the oxidation mass may mass at 160° F.; when oxidation was completed
be permitted to cool, the Oxalic acid which crys the mass was permitted to cool to 90° F. and
tallizes therefrom removed by filtration, and 40 oxalic acid crystals which formed were separated
the mother liquor then employed as hereinabove from the mother liquor. The yield of oxalic acid
described. If desired, the crystallized oxalic acid amounted to 1.653 parts of acid per part of
may be purified by dissolving the mass in water Starch.
containing a small amount of Sulfuric acid at Two Samples of hydrolyzed starch were also
a temperature of about 150 F., permitting the oxidized under the same conditions described in
solution to cool, crystallizing the oxalic acid the above examples, except that in one case a
with slow agitation to permit the formation of wanadium catalyst containing no iron was used
large crystals, recovering the crystals by filtra and in the other an iron catalyst containing no
tion and drying. The filtrate obtained in the vanadium was employed. The results, compared
purification step, which may still contain snme with the results obtained in the practice of Ex
Oxalic acid, may be concentrated and additinna amples 1 and 2, are shown in the following table:
Oxalic acid recovered therefron by crystalliwa
tion. When carrying out the above method con Per cent catalysts
tinuous) v. the glucose and mixed acid solithinn in mother Oxalic acid Percent total
are continuously added at rates such that the liquor acid pro- starch con
-- duced per werted to
vessel contains over 99%, reaction product, this Fe WOs
part of starch oxalic acid
product, being continuously withdrawn from the
vessel to the crystallizer. 0.64 0, 0087 1.653 70. 64
Another suitable method for carrying out my 0.39 0.005 653 70.64
invention adapted for batchwise operation in 60 0.70 None 0.754 32.22
None 0.0025 1. 413 80,38
volves introducing oxalic acid mother liquor re
covered from a previous batch and containing
about 50% sulfuric acid and the vanadium-iron From the above description it will be evident
catalyst to a reaction vessel, adjusting its va that my invention provides a simple and effective
nadium and iron content, if necessary, to with method for substantially increasing the yields of
in the preferred ranges above mentioned, incor oxalic acid produced by the oxidation of carbo
porating additional sulfuric acid therein to make hydrates with nitric acid. Hence, my invention
up for Sulfuric acid lost in the previous batch. will undoubtedly be of great interest to those
adding a solution of glucose to the mother liquor 70 engaged in the production of this product.
thus treated, heating the mass to between about It is to be understood that the iron is not
150° and about 165° F. and introducing nitric present in the oxidation mass as free iron, but
acid into the mass while maintaining the tem as dissolved iron salts such as ferric sulfate, if
perature within the above range until oxidation sulfuric acid is present, or ferric nitrate; the iron
is complete. At the end of the oxidation the 75 content of the oxidation mass is expressed, how
ever, for purposes of convenience in terms of free
2,822,915 3
ferric iron representing the free iron equivalent of permitting the oxidation mass to cool, whereby
the iron salt content of the mass. oxalic acid crystallizes therefrom, and recovering
Since certain changes may be made in carry Oxalic acid from the cooled mass.
ing out the above method without departing from 7. An improved method for preparing Oxalic
the scope of the invention, it is intended that all acid which comprises oxidizing a monosaccharose
matter contained in the above description shall with nitric acid in the presence of sulfuric acid
be interpreted as illustrative and not in a limiting and a mixed vanadium-iron catalyst at a tem
perature between about 150 and 165 F., the
Sense. relative amounts of carbohydrate and nitric acid
I claim: being such that an excess of the carbohydrate is
1. In the method for preparing oxalic acid by 10
oxidation of carbohydrates with nitric acid in catalyst present in the reaction mass, and the amount of
the presence of a vanadium catalyst, the improve being such that the mass contains be
ment which comprises conducting the oxidation tween about 0.001% and about 0.05% vanadium
in the presence of at least about 0.1% ferric and (expressed as WaOs) and between about 0.39%
iron, 5. about 0.8% ferric iron, permitting the mass to
2. In the method for preparing oxalic acid by cool, whereby oxalic acid crystallizes therefrom,
and recovering the oxalic acid from the cooled
oxidation of carbohydrates with nitric acid in the
presence of a vanadium catalyst, the improve 8SS,
8. An improved method for preparing oxalic
ment which comprises conducting the oxidation acid which comprises forming a solution of a
in the presence of an amount of iron equivalent 20 carbohydrate in aqueous oxalic acid mother liquor
to at least about 0.1% ferric iron and not greater obtained from a previous operation and having a
than the amount required to produce a saturated sulfuric acid concentration of about 50%, an iron
solution of iron salts in the oxidation mass at content between about 0.39% and about 0.8%
room temperature. ferric iron and a vanadium content between about
3. In the method for preparing Oxalic acid by 0.001% and about 0.05% vanadium (expressed
oxidation of carbohydrates with nitric acid in the as WOs), forming a mixed acid solution of mother
presence of a vanadium catalyst, the improve liquor and nitric acid, nitroducing a further quan
ment which comprises conducting the oxidation tity of mother liquor into a reaction Zone, heat
in the presence of controlled amounts of iron so ing the mother liquor in the reaction zone to
that the oxidation mass contains between about 3.
between about 150 and about 165 F., adding
0.39% and about 0.8% ferric iron. thereto the carbohydrate solution and the mixed
4. In the method for preparing Oxalic acid by acid solution in such manner as to maintain in
oxidation of carbohydrates with nitric acid in the resulting reaction mass an excess of carbo
the presence of sulfuric acid and a vanadium cat hydrate, whereby the carbohydrate is oxidized to
alyst, the improvement which comprises conduct 35
oxalic acid, maintaining the temperature of the
ing the oxidation in the presence of controlled reaction during the oxidation of the carbohydrate
amounts of iron so that the oxidation mass con between about 150' and about 165 F. and re
tains between about 0.39% and about 0.8% ferric
iron. Covering oxalic acid.
5. In the method for preparing oxalic acid by 40 9. An improved method for preparing oxalic
oxidation of a monosaccharose with nitric acid acid which comprises introducing into a reaction
in the presence of sulfuric acid and a vanadium zone aqueous oxalic acid mother liquor obtained
catalyst, the improvement which Comprises con from a previous operation and having a sulfuric
ducting the Oxidation in the presence Of Con acid concentration of about 50%, an iron con
trolled amounts of iron so that the oxidation mass tent between about 0.39% and about 0.8% ferric
contains between about 0.39% and about 0.8% iron and a vanadium content between about
ferric iron. 0.001% and about 0.05% vanadium (expressed
6. An improved method for preparing oxalic as WaOs), introducing into the reaction zone an
acid which comprises Oxidizing a carbohydrate aqueous solution of a carbohydrate, heating the
with nitric acid in the presence of sulfuric acid 50 mass in the reaction zone to between about 150
and a mixed vanadium-iron Catalyst at a ten and about 165 F., introducing nitric acid into
perature between about 150' and 165 F., the the reaction zone whereby the carbohydrate is
relative amounts of carbohydrate and nitric acid Oxidized to Oxalic acid, maintaining the temperan
being such that an excess of the carbohydrate ture of the reaction during oxidation between
is present in the reaction mass, and the amount about 150 and about 165 F. and recovering oxalic
of catalyst being such that the mass contains acid.
MAXWELL, J. BROOKS,
between about 0.39% and about 0.8% ferric iron,