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Патент USA US2135427

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Patented Nov. 1, 1938
i‘rank W. Corkery,
Grafton, Pa., assignor to '
Pennsylvania Industrial Chemical Corpora
tion, a corporation of Pennsylvania
No Drawing. Application January 12, 1937,
Serial No. 120,192
4 Claims.
This invention relates to the purifying treat
ment of still residues of a particular sort, and to
the further treatment of such still residues to
produce a primarily elastic mass particularly
5 suitable for use in linoleum, mastic tile,,and the
like products. This constitutes a continuation in
part of my copending application Serial No.
88,591, ?led July 2, 1936, and also bears a species
relationship to the invention generically dis
lO closed and claimed in my co-pending application
Serial No. 53,213, ?led December 6, 1935.
The still residue with which I deal is a, still
residue remaining from the treatment of coke
(Cl. 196-13) \
naphthalene. Although there is variation in the
above-noted practice in different coking plants,
commercial still residueusually consists of 70 to
75% crude still residue, or crude still residue and
bottoms, and 25 to 30% pure still residue.
In preparation for an oxidizing treatment. or
in preparation for other uses of the still residue,
I desirably remove sulphonates. This sulphonate
removal I effect by commingling the still residue
with a petroleum, distillate, such as petroleum in
naphtha, mineral spirits, kerosene, ligroin, gaso
line, and- the like, in which sulphates and sul
phonates are relatively insoluble. The sulphates
oven light oil. This still ‘residue contains poly
15 mers of resin-forming bodies in various stages of ‘ and sulphonates may be considered in practical
eiTect wholly insoluble in these petroleum distil- l6
polymerization, heavy monomers, naphthalene, lates
at temperatures not exceeding 80°
and I
and varying percentages of solvents andlsulphon
therefore preferably maintain the solvent mix
ates. It is a dark, viscous, oily substance, de?ci
ture at or below such temperature. The use. of
ent in drying qualities, and of itself possessing any
substantial quantity of any one of the pe
20 but little utility in the arts. As it is commercial
troleum distillates is useful in the removal of 20
' ly available, the still residue may be obtained sulphates and‘sulphonates, but I prefer to utilize
from either of the following operations conducted a volume of petroleum distillate almost double
upon the light oil derived from the gases which the
volume of the still residue, and prefer to use
are evolved in the coking distillation of coal.
petroleum naphtha, which has the least solvent
One such source is the still in which coke
power 'for sulphates and sulphonates. In the ad- 25
oven light oil is puri?ed and fractionated to give mixture, the. other components of the still residue
crude benzol, crude toluol, No. 1 crude solvent are soluble in the petroleum distillate, but upon
naphtha (crude xylol), and No. 2 crude solvent standing the sulphates and sulphonates settle
naphtha. The residuum from this fractionation out. Physical separation of the still residue solu-v
30 consists largely of heat polymers, and is known in tion and the sulphate and sulphonate precipitate 30
the trade as “crude still” residue. 'The fractions may be e?ected in any suitable manner, as, for
from the “crude still,” after. washing with sul
instance, by decantationor by ?ltration. De
phuricacid and neutralization, are. distilled in sirably, the solution, after separation of the pre
what are known in the trade as “pure stills.” cipitate, is agitated, with a small quantity of
35 The residues from the distillation of these frac
sodium hypochlorite, followed by a sodium hy- 85
tions comprise primarily acid polymers and heat droxide wash and water washing, this latter treat
polymers, and comprise also sulphonates. It also ment having the effect of improving the odor of
contains sulphates from acid puri?cation and the still residue.
I may then desirably introduce into the solu
40 neutralization which have not been wholly re
moved by washing. This "pure still” residue nor
tion bleaching clay of any of the well-known 40
mally is mixed in a residue tank with the “crude sorts, desirably in a weight of from 2 to 5% the '
still” residue, so that as commercially available
Weight of the solution, agitate it in the solution,
still residue contains at least the residual prod
ucts from these two types of still dealing with
and ?lter it out. The clay, as ?ltered from the
coke-oven light oil and its fractions.
bpdiesof the still residue, leaving the solution im- 45 '
Usually'there is also mixed in- with these vtwo
still residues ‘in the residue tank a third residue
which comprises bottoms from the distillation of
50 the heavier cuts of No. 1 and No. 2 crude solvent
naphtha. Usually the still residue mixture is
subjected to a distillation for the removal of sol
vents and naphthalene. As commercially avail
able, however, the still residue yet contains a
55 small indeterminate, percentage of solvents and
solution, takes withyit some of the color-forming
proved in color as well as odor, and containing a .
lessened content of impurities. Following such
of these puri?cation steps as are employed,- I
separate the petroleum distillate solvent and the
still residue by distilling off the petroleum solvent 50
either under vacuum or by straight distillation.
Preponderantly, sulphates and sulphonates are
found in the pure still residue, so their presence
in the commercial still residue follows roughly
the percentage of pure still residue to crude still ‘5
ohcrude still residue to bottom, com
prised, in what is obtainable under the simple
designation of still residue, that is, still residue
the solvent grade. This oily,_lower boiling, end
V residue,
'derived from light oil from the gases obtained
during the'coke-oven distillation of coal. For
the following treatment we shall therefore con
" sider a still residue containing no ‘substantial
content of sulphates and sulphonates to be our
starting material, whether they be removed in
by the process above de
10 some manner, such as
scribed, or whether they be initially present in
negligible proportion.’
Puri?cation changes the character of the nor
mal commercial still residue in several particu
15 lars. ' By puri?cation the color of the still residue
is changed from a dull, dark red to a bright.
‘yellowish red. The puri?ed product lacks the
sweetish odor associated with unpuri?ed still resi
due, while retaining the characteristic coal-tar
odor and the burnt odor typical of still residue.
The voscosity of puri?ed still residue is much
lower than that of a still residue before puri?ca
- tion. As typical, I have noted a lessening in vis
cosity from 180 Saybolt seconds at 100° C. to a
viscosity of 100 Saybolt seconds at 100° C. The
25 puri?ed still residue is miscible with most organic
liquids, including the petroleum distillates with-.
, out precipitation or sludge formation. Another
important improvement in puri?ed still residue
over the unpuri?ed material is found after oxida
tion, in that the puri?ed material, as oxidized,
is far more soluble than the oxidized unpuri?ed
material. By purifying the still residue I there
fore not only place it in better condition for use
as a raw still‘ residue, but as a matter of greater
35 importance I prepare‘ it for the production of an
oxidized product of improved‘ solubility.
’Whereas for many uses it is advantageous to
retain and to oxidize substantially the entire ini
tial content of the still residue (sulphates, sul
40 phonates, and the like, being considered as wholly
foreign bodies), for other purposes advantage is
derived by removing a portion of the lower oily
polymers of the still residue prior to oxidation.’
If this topping operation by which a portion of
45 the lower oily still residue polymers are removed
is conducted in situ following the process of puri
. ?cation, the removal of a portion of the lower
of the still residue consists of the aromatic oils
boiling up to about from 275° C. to 290° C., and
an oily substance formed of the dimers of the
resin-forming. bodies (such as coumarone and
indene) in the still residue, which boils from
about 300° C. to about 360° C. It is this oily and
of the ‘still residue which possesses relatively high
unsaturation, and which is, therefore, particu
larly susceptible to oxidation. As a precedent to 10
an effective oxidizing treatment, it is necessary_
that some substantial proportion of the oily lower
boiling end of the still residue be retained-as
that'portion of the still residue which is formed
of higher polymers possesses but relatively slight
unsaturation, and material advantage is not to
be derived by attempted oxidation of it.
I have discovered that for certain purposes,
and chie?y for'use in linoleum and mastic tile,
a lesser elasticity than that obtained by oxidiz 20
ing the total content of the still residue (disre
garding foreign bodies, such as sulphonates,
naphthalene‘and solvents) is desirable. When
the entire true content of the still residue is ox
idized into the state of a solid'up to a desired
melting-pointit has high penetration and elas
ticity. As an example, when the total true still
residue is oxidized to a melting-point of 180° F.,
it acquires a penetration of_ approximately 140
at 77° F. under a 50 gram load. As forming the 30
body of tile of linoleum it then lacks ?rmness
suillcient to support loads without yielding to a
material extent. It is susceptible to penetration
under concentrated forces, such as the. feet of
articles of furniture at which a substantial weight
load is concentrated. For this purpose, there
fore, I have found it desirable to remove a pro
portion of the oily lower end of the still-residue
to provide, upon adequate oxidation, a solid mate
- rial‘ of adequately high melting-point and of mod 40
erate penetration and elasticity, so that as in
corporated in tileor linoleum it may have ade
quate weight-supporting ?rmness. As an exam
pie, the still residue, with about 70% oi’ its oily
lower boiling end removed, when oxidized to a
melting-point of 180° F., acquires a penetration
of only about 30 to 35 at 77° F. under a 50 gram
load. In preparation for oxidation in contempla
tion voi? such use, the extent to ‘which the still
polymer oils may follow sequentially the step of. residue is topped will dependupon the type of
distilling off the mineral spirits used in purify
50 ing' the still residue, and a continued distllaton tile or linoleum which is to be made from the
oxidized product; that is, in accordance with the
which removes the initial solvent content, and load-carrying ?rmness which may be necessary
naphthalene content of the still residue. Con
for it in its contemplated use and to the‘climate
ducting such distillation to remove the oily lower in which the linoleum .or tile'is to be used._
boiling end of the still residue, that part of the
Oxidation of the topped still residue may be
distillation which is conducted at a temperature conducted in accordance with the disclosure-oi.’
at and above 425° F. is desirably conducted un
my co-pending application Serial No. 53,213, ?led
der vacuum and with the use of live steam. If December 6, 1935. Such procedure will be here
the still residue is puri?ed at another time or summarized. The liquid topped still residue is
place, or if puri?cation of the still residuebe dis
00 pensed with, the distillation to remove a portion introduced into a vessel providedwith coils for
circulating steam, or other heating medium, and
of the oily lower boiling end of the still residue
with perforated coils connected with a
1.,is ‘similarly conducted; distillation. being con
blower for introducing air under pressure. De
tinued until the desired proportion of oily lower sirably, the still residue is initially heated to a 65
boiling end of the still residue has been distilled temperature approximating ‘175° F., in order to
over, the distillation at and above 425° F. being
increase the ?uidity of‘ the material, and in order
desirably conducted under vacuum and in the to facilitate the dispersion of air through it.
presence of livesteam.
Air is then introduced in ?nely divided streams
In preparation for use as a raw material, any
the bottom of the vessel, and is passed 70
desired portion of the oily lower boiling end of adjacent‘
upwardly through the body of the still residue.
the still residue may be distilled off. In prepara
tion for oxidation, I desirably remove from 25%
to 75% of the oily lower,boiling end of the'still
residue, as such oily lower boiling end exists after
75 the removal of naphthalene and aromatics of
In so doing I introduce the air under such pres--.'
sure that it is ‘capable, in a dispersed condition,
of penetrating the body of the liquid.
Blowing is continued for a total treating period
of from 2 to 5 days in accordance with the proper
consistency or melting-point of the product for
its ultimate intended use._ Thus for mastic tile
and linoleum _3 to 4 days, giving a melting-point
of around 120° F., "is desirable. For use as an
3 days is desirable, while for
use in making molded articles, and for tile and
linoleum of grades adapted vfor heavy duty, a
treatment of more than 4 days to impart a melt
10 ing-point of 150°‘F. and over is useful.
Throughout the blowing the temperature of
- ‘10
the still residue is progressively raised, as it
becomes possible so to do without blowing oiT
content of the still residue-which it is desired to
15 retain, and as it becomes necessary to do so in
order to maintain the still residue suiiiciently
liquid for the dispersion of air therethrough. In
is not carried
20 upwardly beyond about 325°blown
With blowing carried to any stage the result of
the blowing is an oxidation of the unsaturates of
‘ 2. The herein described method of purifying
tillation of’ the lght
the still residue, giving it drying qualities and
raw aromatic still residue from the treatment of
coke-oven light oil derived in the by-product
coking of coal and containing sulphonates’ of the
light oil aromatics formed by acid puri?cation
and neutralization in the light oil prior to a dis 20.
' '
imately twice its volume of low-boiling aliphatic 25
solvent, separating the precipitated sulphonates
from the solution of sulphonate-freed still residue
in low-boiling aliphatic solvent, and by distilla
tion separating the solvent from the still residue.
3. The herein described method of purifying 80
raw aromatic still residue from the treatment of
in the by-product
oxidized untopped still residue and hard resinous
35 material obtainable by distilling oif all the lower‘
sulphonates of the ~
polymers of the still residue, as well as the initial '
naphthalene and solvent content of the still
residue. Its penetration and elasticity are sub
stantially greater than the like qualities of a true
40 resin, although less than those (of untopped
oxidized still residue.
Considering the puri?ed and topped, vbut un
oxidized, still residue, this is a homogeneous
material, free from curds. Its waterproo?ng
45 qualities are improved. It is soluble in ordinary
petroleum solvents, without
ing and settling the raw still
I an equal volume of low-boiling aliphatic solvent,
separating the precipitated sulphonates from the
boiling aliphatic solvent, and by distillation sep
arating thesolvent from the still residue.
4. The herein described ‘method of purifying
sludge. Its viscosity, or melting-point, depends
upon the stage to which topping is carried. It
commonly employed.
I claim as my invention:
1. The herein described method 01' oxidizing
anequal volume of low-boiling aliphatic solvent,
by distillation separating from the still residue
the aliphatic hydrocarbon solvent and the more
volatile content of the still residue such as naph
and having a lesser elasticity than that result
0 ant from oxidation 01' the total still residue con
tent which comprises precipitating sulphonates
in the still residue by solvent separation in a low
thalene and aromatic solvent content, and by
continued distillation removing‘ a portion and
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