Patented June 27, 1933 1,915,748

UNITED STATES PATENT OFFICE

NIANFRED NIUELLER, OF HAMBURG (NIEDERRHEIND, GERLIANY, ASSIGNOR TO SACHT
LEBEN AKTIENGESELLSCHAFF FijR BERGBAU UND CHEMISCHE INDUSTRIE, O
coLoGNE-ON-THE-RHINE, GERMANY
PROCESS FoR, TIANUFACTURING BARIUM suLPHATE OF DEFINITE GRANULE SIZE
No raWing. Application filed April 22, 1931, Serial No. 532,136, and in Germany April 28, 1930.
This invention relates to the production of which it occurs. In this form it is used as
barium sulphate, the granule size of which is the so-called adulterating spar for litho
capable of being arbitrarily fixed and which pone as well as for pigments in general.
may be chosen of the order ranging from the Hitherto it has been practically unadvisa
is finest granule size up to that equal to coarse ble to use the barium sulphate made accord 60
ly crystalline ground natural heavy spar. ing to the known processes by chemical inter
For many purposes, such as for example, action (permanent white or blanc fixé) for
in the paint industry, a coarser granule is re adulteration of pigments, although this is
quired than is obtained in the case of barium considerably superior to natural adulterating
3 sulphate precipitated by the known proc spar as regards whiteness. The reason for
esses, i.e. so-called permanent white or blanc this is that the use of the binding agent
fixé. Of course, processes are known for which, in addition to the covering power,
increasing the granule size during the pre granule fineness and so forth is decisive
cipitation, for example, for the so-called matt when judging a pigment, is very much high
: goods of commerce, but the granule size of er in the case of ordinary finely granular per ()
this material is still too fine for many pur manent white than in the case of natural
poses. For example, it cannot be used in gground heavy spar.
the paint industry in place of natural ground The object of the present invention is so to
heavy spar. . . change the structure of permanent white
. ..
A V The use of a not too finely granular heavy precipitated from barium salts in the 5.
spar is of importance, more particularly for known manner that it passes over into a
adulteration, i.e. admixing to lithopone. As coarsely crystalline substance and conse
is well known lithopone is a mixture of bari quently assumes the physical properties of
um sulphate and zinc sulphide. It occurs in such a substance as well. -
25 commerce in various kinds which are charac It has been found that blanc fixé prepared 80
terized by a coloured seal according to their in any desired manner may be converted into
zinc sulphide content. “Red seal' lithopone, a coarsely crystalline product if a small con
having a content of 30% zinc sulphide and tent of fusion agent in the form of com
70% barium sulphate, is the kind mostly used. pounds of alkalies and alkaline earths, such
30 This kind may be made in two ways. Either as their oxides, hydroxides, carbonates, chlo
molecular quantities of barium sulphide and rides, sulphides, sulphates and others, is in
zinc sulphate may be allowed to interact with corporated with the finely granular prepa
one another and in this way the so-called ration and the dried blanc fixes is then ignited
purely precipitated material be obtained, or at temperatures of 300° C. to 1000° C. and
35 a lithopone having a higher zinc sulphide above, according as whether it is desired to
content may be made and this may then be obtain a finer or coarser crystalline structure
adulterated with barium sulphate until the for the blanc fixé. A content of about 0.1%
content corresponds to the desired seal. of the fusion agent is already sufficient; how
By adulteration is here understood merely ever, larger quantities of the same may also
40 the admixing of the dry product at the end be used. The water soluble reaction prod 93
of the production process of a pigment or the ucts which are formed during the precipita
subsequent adulteration of the pigment with tion of the blanc fixé may also advantageously
the adulterating spar, and not the chemical be used as fusion agents, these salts being
precipitation of barium sulphate within the only incompletely washed out and the precip
45 pigment, such as is effected, for example, in itate then ignited. In this way up to about 00
the production of lithopone (or other pig 3% of the salts remain in the precipitate.
ments) in the first named manner. The The higher the temperature of ignition the
adulterating spar may be added to the litho more coarsely crystalline is the ignited prod
pone at any desired stage of .the. manufactur uct. Whereas the particle size of ordinary.
50 Ing process. . blanc fixé amounts on an average to 0.001 105
Hitherto only naturally occurring barium mm., the present process provides crystals of
surphate, the heavy spar, was used for the the order of about 0.04 mm. in size.
adulteration, which had been ground to maxi The duration of the ignition amounts ap
mum fineness and usually subjected to a puri proximately to 1-2 hours; the higher the ll.0
55 fication process according to the purity in temperature of ignition the shorter is the
 2 1,915,748
time to be adjusted. It is to be assumed as a sodium sulphate, usually 0.1-0.5%, in actual
measure that the ignition is to be continued combination there with. This adsorbed sul
until the material is sintered. phate is insufficient to produce the effect ob
The ignited product may be allowed to tained by the present invention, i. e., an
cool and then ground; it may advantageously arbitrary variation in the granule size of the 0
be chilled in water. By this means the in barium sulphate; freely admixed and not
candescent hard lumps forth with disintegrate absorbed salt is necessary in order to pro
to powder to a maximum extent, which latter duce this effect. The invention claimed by
is further worked up after Washing. me is limited to the fusion treatment of pre
O The ignition and chilling of precipitated cipitated barium sulphate containing freely
barium sulphate is in itself already known. admixed, as distinct from adsorbed or other
it is new, however, to use these two expe wise combined, fusion agent.
dients, or ignition alone, in the case of blanc What I claim is:
fixes which contains a fusion agent; the effect 1. Process for making barium sulphate of
consists in the fact that the granule size is definite granule size consisting in adding 80
changed. Small quantities of a fusion agent to un
The barium sulphate treated thus is ground washed precipitated barium sulphate, and
and dried in the known manner. igniting at temperatures of 300 to 1000° C.
It is also possible according to this process and above according to the degree of fineness
to make a very finely granular blanc fixe of the crystals desired. - 85
which does not meet, for example, the de 2. Process for making barium sulphate of
mands of the paper industry and frequently definite granule size consisting in adding
represents a bothersome waste product, Val Small quantities of an alkali compound to
luable for other industries, for example, the unwashed precipitated barium sulphate, and
paint industry, in place of adulterating spar, igniting at temperatures of 300 to 1000° C. 90
Eaamples and above according to the degree of fineness
of the crystals desired. - . ..
. (1) 1000 litres of barium sulphide liquor 3. Process for making barium sulphate of
coitaining 135 g. of BaS per litre are stirred definite granule size consisting in adding
up at 50°C. with Glauber's salt solution con Small quantities of an alkaline earth coin 95
Jaining 200 g. of Na2SO per litre until all pound to unwashed precipitated barium sul
the barium sulphide is precipitated and a phate, and igniting at temperatures of 300
small excess of Glauber's sait reinains in the to 1000° C. and above according to the de
solution. 20 kg. of common salt are added gree of fineness of the crystals desired.
and, after it has entered solution, the pre 4. Process for making barium sulphate of 100
cipitate is separated from the liquor con definite granule size consisting in precipi
taining sodium sulphide and sodium chlo tating barium sulphate, incorporating with
ride. Without further washing the barium the unwashed precipitate small quantities of
sulphate obtained the latter is dried and the water soluble alkali salts arising during
ignited at a temperature of 650° C. the precipitation, and igniting the precipi 05
(2) 1000 litres of barium chloride liquor
tate at temperatures of 300 to 1000°C. and
containing 220g. of BaCl per litre are pre above according to the degree of fineness of
cipitated at 50° C. with 1000 litres of a the crystals desired. - -
Glauber's salt solution containing 150 g. of 5. Process for making barium sulphate of
NaSO, per litre, 246 kg. of barium sulphate definite granule size consisting in precipitat 10
being obtained. The precipitate is sepa ing barium sulphate, incorporating with the
rated from the liquor containing sodium unwashed precipitate small quantities of the
chloride, and, without further washing, is water soluble alkaline earth salts arising
dried and ignited for two hours at 700° C. during the precipitation, and igniting the
The still incandescent barium sulphate ob precipitate at temperatures of 300 to 1000° .5
tained in accordance with Examples 1 and C. and above according to the degree of fine
2 may be chilled in water; this brings about ness of the crystals desired.
immediate removal of the fusion agent by 6. In the process claimed in claim 1, chill
:
dissolution and as a result, the grinding ing the ignited barium sulphate in water.
which is afterwards effected in the known
manner is facilitated.
7. In the process claimed in claim 2 chill 120
ing the ignited barium sulphate in water.
I am aware that in Patent No. 1468,867 a 8. In the process claimed in claim 3 chill
process is described in which barium sul ing the ignited barium sulphate in water.
t
phate prepared by precipitation of barium 9. In the process claimed in claim 4 chill
sulphide with a solution of sodium sulphate ing the ignited barium sulphate in water. 125
is thoroughly washed and calcined at say In testimony whereof hereunto affix my
900° C., whereby its bulk is diminished. The signature this 8th day of April 1931.
barium sulphate resulting from the thorough
Washing contains a fraction of a percent of MANFRED MUELLER. 30