Patented Nov. 13, 1934.

1980,338

UNITED STATES PATENT OFFICE

1,980,338
PURFICATION AND BLEACHING OF
WAXES
Arthur Hough, Passaic, N. J., assignor to
Theodor Leonhard Wax Company, Haedon,
N. J., a corporation of New Jersey
No Drawing. Application August 17, 1931,
Serial No. 557,727
(C. 87-19)
2 Claims.
having previously placed in the tank about 750
The present invention relates to certain very pounds
important and valuable discoveries relating to the fourth of water (corresponding to about One
purification and bleaching of waxes, and par of the weight of the wax). In order to
ticularly beeswax. Actual use of the process has preserve this ratio of water to wax during the
proven it to be highly economical and very prac treatment, I prefer to heat the mass by means of 60
closed steam coils. The water and wax are heated
tical.
The invention will be described in detail in its up to a temperature preferably about 90 to 95 C.
(say 93° C.), i. e. a little below the boiling point
preferred form, in connection with beeswax, but of water. I add the dilute crude phosphoric acid
it is applicable also to carnauba wax and, I be
lieve to various others. mentioned above, in amount equal to about 2% 65
I have found that phosphoric acid, either the (for example) of the wax (=0.6% actual H3PO4
ortho or the meta compound has a very useful based on the wax), and stir vigorously, by One
action on the wax, completely removing many in of the types of motor driven stirrers known as
“lightning' mixer, whereby a most intimate mix
purities, both those in plain suspension and those
held in a colloidal condition. The impure Wax, ing of water and acid and wax is obtained. The 70
melted and subjected to the influence of phoS initial mixture of water and acid i. e. 60 pounds
phoric acid becomes clarified in a manner quite of the crude dilute acid in 750 pounds Of Water
impossible of attainment with any other acid represents approximately a 2.4% Solution of
which has heretofore been used. I am aware that HaPO4. The mixing should proceed for about 10
20 minutes, at about 90 to 95° C., when the stirring is 75
in the past, sulphuric and hydrochloric acids have stopped
been tried for this purpose, and while they clarify and the tank may be covered up (to pre
the wax better than plain settling over Water, the vent rapid cooling) and allowed to stand for sev
Wax having been melted and stirred with the Wa eral hours, when the wax will be found to be
ter, yet I have found that the results obtainable completely clarified. All suspended and colloidal
25 matter will have been removed, and thrown to the 80
by the use of phosphoric acid are so far Superior
bottom of the wax and largely into the acidulated
than anything obtained by prior methods, as to be
revolutionary. Water, the wax will be found to be what is known
I have found during my researches and in ac as pure refined wax, and of a clear, almost trans
parent character. This remarkable effect can be
tual plant practice, that the variety of phosphoric
30 obtained by the use of very little of the phos 85
acid known as "crude' is better for my purpose phoric
than the chemically pure acid, one particular actuallyacid, and as stated above, the crude acid
works better than pure H3PO4. This . .
sample of this crude phosphoric acid analyzing may be due to the coagulating effect of the iron,
as follows: aluminum and other salts (impurities) dissolved
Per cent in the crude phosphoric acid, these salts will be 90
35
P2O5 ------------------------------- - 21.00 found, together with the impurities of the Wax, in
(Equal to H3PO4---------------------- 29.18) the water under the clarified wax. Some of the
Al2O3 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - O 64. impurities may be in the bottom layer of the Wax.
Fe2O3--------------------------------- . 92 Most of the molten wax can now be decanted 95
40 SO3---------------------------------- 69 in a clear condition, and the bottom layer of the
CaO --------------------------------- 93 wax can be retreated or otherwise purified.
Organic material---------------------- . 10. In this example I have referred to the use
This analysis covers an average grade of crude of 60 pounds of the crude phosphoric acid in the
phosphoric acid just as it is obtained from the treatment of a particular grade of wax. In other
cases I have used much less, Say 25 or 30 pounds 100
45 decomposition of phosphate rock, and without of the acid (with 3000 pounds of wax and 600 to
any further purification. This grade is of course 800 pounds of water), while securing very satis
of the lowest market value (i. e. is the cheapest,
for a given amount of actual H3PO4), and is factory results. These variations would corre
therefore very economical to use for the present spond to acid concentrations of about 1 to nearly 05
50 purpose. This is given merely of a highly suit 4%. W
In commercial practice after treatment with
able phosphoric acid, but the invention is not. phosphoric acid, and stirring, the Wax begins to
limited to acid of this analysis.
As an example of the process of purifying the clear immediately, the impurities settling down
through the bulk of wax towards the bottom. If
crude wax, I give the following as an illustration: left to settle long enough, the impurities will all 10
55 I melt 3,000 pounds of the wax, in a large tank
 2 1,980,388
go to the very bottom of the wax, appearing as of the tub, the wax flowing into a wash tank
a spongy matter, with such inorganic substances
as may be present and of a higher specific gravity placed at the side of the bleach tub. This wash
tank contains water, acidulated with HaSO4 to an
than wax or water, going to the bottom of the extent of about .1%. . .
vessel. In practice at the works, I allow the wax . I have referred in this example to temperature 80
to settle over night as a matter of convenience. at which the mixture of wax, acid, permanganate
The wax may be treated at about 4 P. M. and and water should be at the start, about 65° C. To
then covered up. The tank being of very thick explain this point. The important point to look
wood, when covered, I find the wax and water to is the maximum temperature to go to during
0 will hold the heat till the following morning, bleaching, and for the very best results, I have
When operations commence. Thus I may allow found this maximum temperature should not ex
the wax to stand therefor a matter of about 15 ceed 80° C. Now, in order to determine the tem
hours, although perhaps the settling is complete perature at which to start the process to reach
in much less time. this temperature, we have of course to consider
5 Bleaching the waac.-The clarified wax, is now the following:-Heat of reaction (KMnO4 oxida
ready to be bleached. This may be done by Way tion value or organic impurities in wax), specific
of example in an apparatus as follows: A wooden heats of Wax, Water, and acid, and weights of
tub, measuring about 50 inches diameter, and 60 same. In actual practice I find that in wood
inches high (inside measurements) is fitted with tubs where radiation factor is low, I can start
20 a powerful stirrer. This stirrer may conven the mixture at about 65° C. At the same 95
iently be of the “turbo' type of impeller, 30 inches with
in diameter having 12 blades placed at an angle a waxitsuch
time, must be remembered that in the case of
as a very high grade of Chilian bees
of about 30 degrees. This stirrer can be fitted Wax, or light Cuban beeswax, the organic impuri
on a steel shaft 2% inches in diameter and cov ties are so Small that much less KMnO4 is re
25 ered with lead to a point as high as the top of quired and consequently less heat of reaction de 00
the tub. The stirrer itself may be cast in one velops. In Such a case, the charge may be as
piece of antimony-lead alloy (preferably 5% an high as 70° C. at the start, and it will not exceed
timony and 95% lead). The shaft is held in 80° C. at the finish. The pilot laboratory test
bearings some distance apart to give rigidity to Will determine this point. Another thing of im
30 the driving equipment. The shaft revolves at portance. A charge should always be allowed 105
about 150 revolutions per minute, the action of to proceed under its own heat of reaction. There. '
the stirrer being preferably downwards to en is a cuirious phenomenon in this connection. If a
sure perfect agitation or dispersion of the liquids. bleach
Obviously this apparatus is given merely by way checkedisbyin any progress, and the temperature be
method of cooling, and then
85 of example. raised again by heat from closed or open steam 110
About 1000 pounds of water (ordinary tap wa or hot water coils, the bleach is not good. The
- ter will do), are placed in the tub, heated to . . charge, starting at the low temperature should
about 65° C., and about 160 pounds of the crude be allowed to find its maximum temperature by
dilute Orthophosphoric acid added, the stirrer is its own heat of reaction. This has been shown
40 Started and a few seconds mixing given. This in commercial runs. - 115
gives a dilute phosphoric acid solution of about. The time required to effect a bleach, after all
4.7% strength. Then 1250 pounds of the clarified ingredients are in the tub and stirrer started,
beeswax is added, this latter at a temperature is generally about one hour. This however may
of about 65° C. This represents about 3.8% of vary according to the grade of wax. V.
45 acid
actual H3PO4 relatively to the wax. The wax, The object of this acidulation will be explained 120 .
and water are now stirred continuously and later. It is important to have this wash water
into the mixture is run a solution of 50 pounds slightly acid, if it is not, good results are difficult.
of potassium permanganate in 300 pounds of wa to obtain. The wax being now in the slightly
ter at about 70° C. which has been slightly acidi acidulated water, best at about 80 C., by means
50 fied by H3PO4. The bleaching action starts im of a rapid stirrer (such as wastised for the clari-125
mediately, and is allowed to proceed until the fication of the crude wax) the wax is given a
end point of the bleaching is reached. This thorough washing for example at about 80° C. for
point is ascertained by testing the mixture in the say 15 minutes. This may be called the “pre
following manner. A sample is dipped from the wash' and is very important. After this pre
65 tank and allowed to stand in a beaker for a few wash, the waxis allowed to settle, and the wash 130
minutes. If the end point is reached, it will be water is then runoff by means of a cock at the
found that the clear wax will rise to the top, the bottom of the wash tank. Then another lot of
oxides of manganese (product of reduction of per water, slightly acidulated with HaSO4, also at
manganate) will fall to the bottom, and an in about 80°C. is run in, and about two pounds of
60 termediate zone of a pinkish solution will be 93% HaSO4 is added, this acid should be diluted 135
apparent... If the endpoint is not reached, it will to 20% or less, before adding to the wax and
be seen that the wax does not separate well, and water, as strong. H2SO4 coming into contact with
the process must be continued till such time as the bleached wax may affect its color. Brisk
another similar -test gives the desired result.
When treating beeswax of average grade, this agitation is now continued and about three
pounds of 100-volume hydrogen peroxide added. 140
-
may require about an hour. When such end 25-volume H2O2 is used, then proportionately
point is reached, the charge in the tub should If
be allowed to settle for a few minutes, when the more of it must be added. It will be found after
15 minutes stirring, that the wax has assumed
bleached waxwill be ready to be removed from the a fine white color and need only be allowed to
o tion.
mother liquor. The latter is still acidS in reac Settle, the acid water drawn off, and another 145 ,
This removal can be accomplished by running plain wash water at about 80° C. run into the
hot water into the bottom of the tub, (without tank keeping the water only on the acid side
first drawing of the acid solution) thereby rais ‘due to theorange
to methyl test to prevent actual alkalinity, . .
is ing the level of the wax to an outflow in the side this"stirred well andalkalinity
natural of, the water, and
allowed to settle for a few 150
 1,980,838 3
hours when the white wax may be drawn off by. 'ide of hydrogen when Dashing bleached upac.-
a tap at the side of the tank, or preferably by When the wax is passed from the bleacher to
displacement as described above, and this wax is the wash tank it may and generally does carry
a minute quantity of permanganate of potash
now found to be highly bleached. . v
The wax may then be given One or more addi and also a trace of the oxides of manganese in 80
suspension. H2O2 in this case acts as a reduc
tional washings with distilled water, (preferably ing
at about 80° C.) the object of which is to remove agent, immediately reducing both these re
all (or substantially all) acidity, without running agents to the lowest. Oxides of manganese, and
any risk of any alkaline reaction. This would these are immediately taken up by the H2SO4 to 85
O be an advantageous addition to the process, if product MnSO4 which of course is readily soluble
a supply of distilled water is available, but many in the water, and the highly bleached and per
commercial runs, without the washing with dis fectly white wax is the result. Other reducing
tilled water have given very satisfactory results. agents may be used as sodium bisulphite SO2
This wax which preferably has been kept molten etc., but these do not act nearly so well as H2O.
5 throughout the treatment, can then be run into Importance of the pre-wash-When the wax
molds, and allowed to Solidify by cooling. has been bleached, it will contain iron and man
In the several Washings, I preferably use a ganese salts and probably, other salts present in
temperature about 80° C. this procedure should the reagents at the start. The pre-Wash is to
be followed in all washing operations. At about remove such salts, which it does most effectually
20 this temperature, the wax is very fluid and agi and the acid present of course prevents such salts
being acted upon by natural alkalinity of the
tates and washes better than if at a lower tem water
perature. It is inadvisable to heat to a higher which would have the effect of "fixing’ the
temperature, although no great amount of harm iron and manganese in the wax, and imparting
will result. It must be kept in mind that when to it the characteristic color of manganese and 00
25 beeswax is bleached, it is easily thrown off a iron on Organic matter. Wax, like cellulose, has
shade or so in color by too much heating, so it a great affinity for these substances.
is better to keep it at a reasonable temperature, Heretofore processes of bleaching wax and
and to avoid temperatures much above 80° C. particularly beeswax depended on the use of ox
While I have given proportions and quantities, idizing agents, Such as chromic acid, bichromate
3. in the specific example, which are highly satis potassium or Sodium and Sulphuric acid, perman 05
factory, I do not limit the invention to these, ganate of potash and sulphuric acid, perborate of
since the same can be varied between rather soda and many others, are well known but the
wide limits, without departing from the inven performance of these reagents is utterly different
tion. These figures show the preferred amounts from the action of phosphoric acid, and do not
35 when the crude wax is of average grade of purity. give comparable results. 10
When a more impure wax is being treated, I When H2SO4 is used with KMnO4 for bleach
would preferably, use somewhat larger amounts ing wax, by certain processes previously sug
of the chemicals even up to double the amounts gested, the acid to sufficiently decompose the
given above, or even somewhat more, and the KMnO4 has to be of such strength as to actually
40 aimount of water can remain as given above. attack some components of the wax, injuring its 15
Similarly when using a crude Wax leSS impure quality. The action is so violent as to produce
than average grade, less of the chemicals can be violent frothing in the bleach tub. As an in
used, even downl to half the amounts above given. stance of this I may state that in a bleach tub.
The amounts of water given in the several of the dimensions given above, only 600 pounds
45 chemical treatments can also be varied between of wax could be used in a charge, by the old way 120
wide limits, but the quantities stated above will (KMnO4. plus H2SO4), due to frothing. By the
be found very satisfactory. new way charges of 1250 pounds are regularly
It is important to place the phosphoric acid in run, in this tank Without any sign of frothing.
the water in the bleach tank before running in Phosphoric acid is the one acid that (within the
50 the crude clarified wax. If this is not done, the ranges of concentration given above) does not at-125
natural alkalinity of the water may emulsify the tack the true Wax in any Way, and therefore the
wax, and this, whilst not very serious may easily product contains the original values of myricin,
prevent subsequent separation for Some time, cerin, and cerolein. This is a great advance over
and thereby delay the process. It is very in the prior art. Moreover, a large portion of the
55 portant (as has been found in commercial tests) phosphoric acid may be recovered and used over 130
to acidify the permanganate solution with phos
again as it undergoes no change during the proc
phoric acid before running it into the wax. If
eSS, and the manganese oxides may also be largely
the permanganate is not acidified, but run. On
recovered and marketed or reworked into KMnO4.
to the wax even when this is mixed with the To sum up this new process of firstly clarifying
60 phosphoric in the bleach tub, there may be athe crude wax, by treatment with phosphoric 35
local alkalinity arising at the instant the acid and then bleaching by this new process it is
KMnO4 solution strikes the Wax, which may believed to be an important advance in the in
cause an emulsion, which would delay the dustry. . .
process.
If this water in the Washing steps be not acidi
I have found that the crude and impure phos
phoric acid is not only Superior to the pure acid 140
fied before the wax is run into it from the bleach in the pre-treatment process, but also in the
er, the wax carrying practically no acid from actual bleaching process. I am using and prefer
bleacher, striking the large volume of water of to use, the crude acid with permanganate. The
natural alkalinity, this alkalinity has the well iron, aluminum and calcium compounds in the
known effect on wax of causing a "souping' and crude phosphoric acid (all of which are soluble, 145
yellowing of the bleached wax, and if this hap to. Some extent at least), may have some useful
pens the White color cannot be regained. In other effect in the process. -
words, once bleached, wax must not come into I have referred above to the use of potassium.
contact with even the faintest trace of alkalinity. permanganate. Other permanganates such as
75 Use of further amount of sulphuric and peror the sodium compound, can also be used. 5,
 4 1980,888
If it is desired to recover the phosphoric acid 1. A process of treating vegetable and/or afi
in the displacement step without dilution, then in mal wax to purify the same, which comprises agie
place of the hot water mentioned for raising the tating the wax while in contact with hot water,
level of bleached wax, Some of the phosphoric with phosphoric acid of about 1 to 8% strength,
5 acid from a previous bleaching run may be emi said acid containing soluble iron and aluminum 80
ployed for this purpose, this preferably being hot, compounds, at not considerably above the normal
say 80 C. In this way, the phosphoric acid may boiling point of Water, then settling and separat
be used for several cycles, before it is unfit for ing the aqueous liquid and impurities and the
use. To start this cyclic operation, of course
10 enough phosphoric acid must be on hand for the
refined wax from each other.
2. A process of bleaching wax which comprises 85
displacement of the bleached wax of the first treating the molten wax with an acid mixture
batch, but after this, there will be plenty of the comprising a permanganate and phosphoric acid
acid from previous runs to carry on. Great econ and being diluted with many times its own weight
omy results from this procedure, as for several of water, while warm, and containing soluble iron
5 cycles only the mechanical losses of acid have to and aluminum compounds, and agitating until 90.
be compensated for by addition of fresh acid. the bleaching is sufficiently accomplished.
I claim: ARTHUR HOUGH.

20 95.

100

: 36 105

110

115

45. 120

125

30

35

140

70 45

s 50