Patented Oct.

29, 1935
2,019,415

UNITED STATES PATENT OFFICE

2,019,415
ALUMINIUM FORMATE AND PROCEss oF
MAKING THE SAVE
Oskar Jochem, Greiz-Dolau, and Theodor Hea
nig, Greiz, Germany, assignors to firm Zschim
mer & Schwarz Chemische Fabrik Döllau,
'Greiz-Dolau, Germany
No Drawing. Application April 2, 1933, Serial
No. 665,840. In Germany April 18, 1932
4. Claims. (C. 260-11)
The object of this invention is to make a solid
aluminium formate recrystallizable from Water fatty acids
acids with the corresponding free fatty
in excess and leaving the salt solution, thus
Solutions and the product thereof. acidified, to itself, without evaporating down, at
The aluminium salts of the lower fatty acids, the Ordinary temperature for some time, if neces
for example aluminium formate and aluminium sary with agitation.
acetate, are mainly employed for impregnation minium salts may beInobtained this way, crystalline alu- 5
from a solution
in the textile industry and for pharmaceutical Of aluminium formate of a specific gravity of
purposes: They are principally on the market 1.045 and from a solution of aluminium
0.
in the form of fairly dilute aqueous solutions, of a specific gravity of 1.015. According acetate to the
Such as, for example, aluminium acetate in the observations which have been made up to the 10
form of a 7.5 to 8% solution. Repeated attempts present, these concentrations ought not to be
have already been made to manufacture con considered as the minimum concentrations nec
centrated solutions or even solid products of the essary for the success of the proceSS. In prac
s
aluminium Salts of lower fatty acids. So far, tice, starting solutions of higher concentration
however, these attempts have failed to produce are preferably employed, for example, a solution l8
Satisfactory results, firstly because in the con of aluminium acetate of a specific gravity of
centration of the solutions turbidity and deposits 1.075 to 1.100. Complete separation of the salts:
frequently Occur, and secondly because the evap present in the starting solutions does not take
Oration and drying causes decomposition and es place, but the mother liquors may be employed
20 cape of free fatty acids. Furthermore, the Solid
end products obtained by the processes known again. The excess of free acids may be selected 20
as desired within Wide limits.
heretofore were generally either not at all Solu It has further been found that, by using suffi
ble, or Only partly soluble, in Water. ciently strong aqueous aluminium formate Solu
It has already been proposed to manufacture tions, water-soluble
25 Water-soluble crystalline aluminium formate by mate may be obtainedcrystalline aluminium for
even without the addition 28
evaporating an aluminium formate Solution in of free formic acid. Apparently, aluminium
the presence of an excess of formic acid until formate forms slightly Supersaturated Solutions,
a film appears and leaving the solution to crys which separate crystalline aluminium formate
tallize at a temperature of 25-30° C. The crys
30 talline aluminium formate So obtained cannot only when they are left to themselves for some
be recrystallized from an aqueous Solution, and time at the ordinary temperature, if desired with
agitation.
30
obviously, therefore, it is not stable in aqueous Aluminium formate Solutions. With a Specific
solutions. In this known manner of manufac gravity of 1.100 only exhibit slight crystal for
35 ture a considerable expenditure of heat is neces mation after several Weeks When no free formic
sary and loss of formic acid occurs. This process acid is added. The specific gravity of 1.100 may
has not obtained any practical importance. therefore be regarded as the minimum concen
It has furthermore been proposed to manufac tration for the manufacture of aluminium for
ture water-Soluble basic aluminium acetate and mate Without the addition of free formic acid.
40 aluminium formate by drying the aqueous Solu Aluminium formate Solutions of higher Concern
tions of these aluminium Salts in a finely atom tration yield large quantities of crystalline alu- 40
ized form. Even in the case of this process, it is minium formate even in a short time.
not possible to work Without considerable expen The adjustment of the aluminium. Salt Solu
diture of heat for the evaporation of the large tions to the desired specific gravity may be ef
45 quantities of water, and furthermore a compli fected by the reaction of suitable quantities of
cated and expensive apparatus is required for aluminium sulphate, calcium carbonate, and the 4:
this purpose. In this process also no crystals are
lower fatty acids in question.
obtained but only more or leSS finely-divided dry The separation of the crystals from the
residues, which still contain all the impuritiesaluminium salt solution may be assisted by add
50
of the Original Solutions. ing slight quantities of the desired crystalline
It has now been found that aluminium salts aluminium salt as inoculating Substance, if de- SO
of the lower fatty acids, more particularly alu sired after the addition of the free fatty acid.
minium acetate and aluminium formate, may be The crystal formation is likewise promoted by
manufactured without the expenditure of heat constant or occasional agitation.
and without loss of fatty acids, by mixing aque
ous solutions of the aluminium salts of lower beThe crystalline aluminium salts obtained may
readily separated from the mother liquor by 35
 2 2,019,415
filtration. The aluminium formate may be line aluminium formate as inoculating substance
washed without difficulty with water, dried and tion.and is then left to itself with Occasional agita
recrystallized from Water. After 65 hours, 2580 grams of crystalline
The mother liquors remaining after the sepa aluminium formate of the same composition as
ration of the crystals may be employed again in Example 3 will have separated Out. 5
for new mixtures for the manufacture of crystal The present invention represents a consider
line aluminium salt, if desired with the free fatty able technical advance, because by means there
acid contained in the said mother liquorS. of it is p0SSible to obtain aluminium Salts of the
Eacamples lower fatty acids, such as for example aluminium
O formate and aluminium acetate, in a crystalline 10
1. 100 litres of a 7.5 to 8 per cent. Solution water-soluble form on a technically satisfactory
of basic aluminium acetate is mixed with 50 Scale from aqueous Solutions.
kilograms of glacial acetic acid, and is left to We claim:
itself for three days at the ordinary temperature 1. The method of preparing Water-soluble
With constant or occasional agitation. The fine crystalline aluminium formate which comprises lis
ly crystalline aluminium acetate which separates adding, at Ordinary temperatures, formic acid
out is filtered off. Yield: 2 kilograms. to an aqueous aluminium formate Solution of at
2. 100 litres of an aluminium formate Solution least 1.045 specific gravity, and immediately
of a specific gravity of 1.100 is mixed with 15 thereupon leaving the acidified solution to itself
kilograms of 85 per cent. formic acid and 1 kilo at Ordinary room temperatures for some time 20
gram of crystalline aluminium formate, and is with agitation, and separating the crystals from
agitated for three days at the ordinary tempera the mother liquor.
ture. The crystalline aluminium formate de 2. The method of preparing water-soluble
posited is separated by filtration, Washed with crystalline aluminium formate which comprises
25 Water and dried in the air at 50° C. Yield: 3 preparing, at ordinary temperatures, an alu-25
kilograms. minium formate solution of at least 1.100 specific
3. 10 litres of an aluminium formate Solution gravity and leaving the Solution to itself to
adjusted to a specific gravity of 1.152, the crystallize without application of heat thereto.
analysis of which gives 84.4 grams Al2O3 and 3. The method of preparing water-soluble
30 201 grams HCOOH per litre, is left to itself at the crystalline aluminium formate which comprises 30
ordinary temperature with Occasional agitation. preparing, at Ordinary temperatures, an alu
After 120 hours, 50 grams of crystalline alu minium formate Solution of at least 1.100 specific
minimum formate will have Seperated out, the gravity, adding a small quantity of crystalline
analysis of which gives 12.54 per cent. Al, 62.42 aluminium formate, agitating for SOme time at
3 5 per cent. H.COOH and the remainder 25.04 per ordinary temperatures and separating the crys-35
cent. Water, and which thus corresponds to the tals from the Solution, the entire process being
formula A1(HCOO)3.3H2O. carried out without application of heat.
4. 10 litres of an aluminium formate solution 4. Solid aluminium formate of the formula,
adjusted to a specific gravity of 1.220, the Al(HCOO)3.3H2O, exhibiting the property of re
40 analysis of which gives 125.5 grams Al2O3, and Crystallizing from aqueous solutions. 40
336 grams HCOOH per litre, is mixed at the OSKAR JOCHEMI.
ordinary temperature with 50 grams of crystal THEODOR HENNIG.