U.S. patent number 3,668,110 [Application Number 05/084,883] was granted by the patent office on 1972-06-06 for pitch treatment means.
Invention is credited to Louis A. Joo, Thomas W. Martin, Frederick L. Shea.
United States Patent |
3,668,110 |
Shea , et al. |
June 6, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
PITCH TREATMENT MEANS
Abstract
A spinnable pitch, useful in the manufacture of carbon filaments
of continuous lengths, is prepared by the multiple solvent
extraction of pitch, first by trituration of pitch particles with a
low-boiling, aromatic solvent in which the bulk of pitch particles
is essentially insoluble -- then by dissolution of the pitch in a
solubilizing solvent, filtration, and evaporation of the
solvent.
Inventors: |
Shea; Frederick L. (Johnson
City, TN), Joo; Louis A. (Johnson City, TN), Martin;
Thomas W. (Elizabethton, TN) |
Family
ID: |
22187817 |
Appl.
No.: |
05/084,883 |
Filed: |
October 28, 1970 |
Current U.S.
Class: |
208/45 |
Current CPC
Class: |
C01B
32/00 (20170801); D01F 9/145 (20130101) |
Current International
Class: |
D01F
9/145 (20060101); C01B 31/00 (20060101); C01b
001/07 (); C10c 003/08 () |
Field of
Search: |
;208/45,6 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: O'Keefe; Veronica
Claims
1. A method for the preparation of a spinnable pitch which
comprises
a. grinding a pitch into small particles;
b. contacting the particles with an essentially aromatic or
equivalent solvent to dissolve a total of about 10 to 30 percent
therefrom;
c. separating the solvent and the insoluble particles;
d. extracting the particles with a solubilizing solvent in
sufficient quantity to dissolve at least 45 percent of the pitch
based upon the original quantity of starting pitch;
e. filtering the resulting mixture and
2. The process of claim 1 wherein the contacting step, b, is
carried out at from about the freezing point of the solvent to
about the softening point
3. The process of claim 1 wherein the extracting step, d, is
carried out at from about the freezing point of the solvent to
about the reflux
4. A method for the preparation of a spinnable pitch which
comprises
a. extracting the pitch with a solubilizing solvent in sufficient
quantity to dissolve at least 45 percent of the pitch;
b. filtering the mixture;
c. evaporating the solvent from the resulting filtrate;
d. grinding the resulting pitch into small particles;
e. contacting the particles with an essentially aromatic or
equivalent solvent to remove a total of about 10 to 30 percent
based upon the original quantity of starting pitch therefrom;
5. The process of claim 4 wherein the contacting step is carried
out at from about the freezing point of the solvent to about the
softening point
6. The process of claim 4 wherein the extracting step is carried
out at from about the freezing point of the solvent to about the
reflux temperature of the solvent.
Description
BACKGROUND OF THE INVENTION
Carbon fibers have been produced from organic polymer fibers such
as rayon or polyacrylonitrile by oxidation and carbonization of the
fibers. The same process has been found to be applicable to
manufacture carbon fibers from filaments of polyvinyl chloride,
polyvinyl acetate, blown asphalt, and petroleum pitch.
Otani, U.S. Pat. No. 3,392,216, July 9, 1968, discloses and claims
a method for the heat treatment of several of these pitch-like
materials, particularly polyvinyl chloride. The Otani method
involves heating the starting material to 300.degree.-400.degree.
C. in an inert atmosphere to raise the softening point and improve
the molecular weight range of the pitch-like material.
Coal tar pitch is particularly difficult to use because of the
presence of an insoluble second-phase material which must be
removed prior to spinning. If allowed to remain when the fiber is
drawn from the spinnerette, the particles of second-phase material
will form stress points in the filament which tend to lower the
strength of the filament. Nodules on the surface of the filament
will render the filament unacceptable for use in certain
applications.
More recently a method has been devised for treating a coal tar
pitch to enable the pitch to be spun into continuous lengths
capable of being oxidized and carbonized into commercially
acceptable carbon fibers. Such treatment includes (1) dilution of
the pitch with quinoline or light creosote oil, (2) filtration, (3)
evaporation of the diluent, and (4) heat treatment of the pitch
within the range of about 280.degree.-305.degree. C. until a
softening point of 230.degree.-260.degree. C. has been attained,
usually from 40 to 140 hours. The pitch can then be spun, oxidized,
and carbonized as in the prior art. This method leads to a
relatively clean pitch of about 80 percent carbon yield after
appropriate processing of the spun filament which will form 0.5-10
mil continuous filament.
These carbonized filaments have a tensile strength of 80,000 to
130,000 psi, a volume resistivity of 1,280-1,600 micro-ohm inches,
and an apparent density of about 1.65 g./cc. They are useful as
substrates for boron deposition, and as fillers for carbon-carbon,
carbon-resin, carbon-metal composites and other similar
applications where filamentary carbon is conven-tionally and
advantageously employed.
This invention relates to an improved method of preparing a
spinnable pitch-like material from pitches of petroleum, coal tar,
and the pyrolysis of organic polymers origin.
More particularly this invention relates to a method of preparing
such pitch-like material without subjecting the pitch precursor to
heat treatment to raise the softening point, thus avoiding the
potential for second phase carbon formations.
Fibers prepared from the pitch and oxidized and carbonized in the
usual manner have improved characteristics.
SUMMARY OF THE INVENTION
By the process of this invention, a pitch from coal tar or
petroleum, petrochemicals and the pyrolysis or organic polymers is
(1) fabricated into small particles capable of being acted upon by
an appropriate solvent to remove therefrom low boiling, low
molecular weight material; (2) the resulting particles are
contacted with such an essentially aromatic or equivalent solvent
to remove such low boiling, low molecular weight materials at a
temperature from about ambient room temperature to about the
softening point of the pitch in contact with the solvent; (3) the
particles are separated from the solvent; (4) the particles are
then extracted with a solubilizing solvent; (5) the resulting
suspension is filtered to remove the insoluble solid materials
therefrom, and (6) the solvent of the second extraction is
evaporated from the resulting filtrate to yield a spinnable pitch.
In an obvious alternative, steps 1, 2, and 3 are removed until
after the performance of step 6. That is, (1) the raw pitch is
extracted in a solubilizing solvent; (2) filtered to remove the
solid materials therefrom; (3) the solvent is removed by
evaporation; (4) the resulting solid or liquid filtered pitch is
ground if necessary; (5) extracted by an appropriate solvent to
remove the low-molecular weight components; and (6) separated from
the extract. The pitch, when prepared by either of the above
methods, need not be subjected to heating over long periods of time
and is of a physically more uniform nature with respect to
softening point and homogeneity than is a heat treated pitch. The
filaments manufactured therefrom when carbonized to 1,200.degree.
C. or above are stronger than those prepared from heat treated
pitches.
DETAILED DESCRIPTION OF THE INVENTION
Otani, in Japanese patent specification No. 2511/69, discloses a
method for the preparation of a spinnable pitch from coal tar. By
the method of the patent, coal tar pitch is either melted or
solubilized in chloroform and filtered to remove the second-phase
material. It is then destructively distilled at a temperature not
exceeding 250.degree. C. for several hours and then vacuum
distilled at about 300.degree. C. Otani states that the
distillation step accomplishes the removal of low molecular weight
components.
By the herein-described method, only selected low molecular weight
components, only those soluble in benzene or equivalent solvents
are removed. Additionally, there is no thermal rearrangement,
polymerization, or aromatization of the coal tar pitch generally
found as a result of any heat treatment process. This method
affords a product particularly suitable for spinning, oxidizing,
and carbonizing to yield a superior filamentous product.
The first step of the herein-described method is to mechanically or
otherwise form the pitch into small particles, of the order of -100
mesh. This can be done most conveniently by grinding or milling
solid pitch or by nebulizing or atomizing a molten pitch and
rapidly cooling the droplets to below their softening point so as
to prevent coalescence. This nebulization can be accomplished in
the presence of the aromatic or equivalent solvent useful for the
subsequent process of this invention.
The above-formed pitch particles are then extracted by a selected
solvent in such a quantity that from about 10 to about 30 percent
of the pitch is extracted into the solvent, the soluble portion of
the pitch being the low molecular weight components thereof. The
choice of solvent and solvent volume is determined by the desired
softening point range of the final pitch product. As for example, a
pitch solubilizing solvent, quinoline, used in a solvent to pitch
ratio of <1:1 (V/V) is adequate and a non-solubilizing solvent,
benzene, in a >1:1 (V/V) ratio is satisfactory to the practice
of this invention. It is preferred to use a solid to solvent ratio
of about 1:5 (V/V) when benzene is used as a solvent. The
extraction can be carried out at from about the freezing point of
the solvent to about the softening point of the pitch. Ideally,
since the solvent can be recovered and reused, safety and economics
dictate the use of a relatively large volume of solvent at or about
room temperature. We have found that about 1-10 volumes of benzene
per volume of pitch is capable of performing the extraction
depending upon the temperature at which the extraction is carried
out.
The solvent and solid pitch are then separated by filtration,
centrifugation or the like separative means. Preferably, any
residual solvent contained in the pitch is removed therefrom prior
to further treatment of the pitch such as dissolution of the pitch
in the second solvent by the method of this invention. This solvent
removal can be effected by the usual vacuum stripping or
evaporative techniques carried out at or below atmospheric
pressure. It is advantageous to use vacuum removal of the solvent
in order to raise the relative vapor pressure thereof.
The resulting solid pitch particles are then dissolved in a
sufficient quantity of a pitch solubilizing solvent to dissolve at
least 45 percent of the pitch based upon the total quantity of
starting pitch. This dissolution can be accomplished at from the
freezing point to the reflux temperature of the solvent.
The solvent useful for this dissolution can be the same or a
different solvent from that used in the first extractive step. If
the solvent is the same, it is obvious that a greater quantity of
solvent will be necessary and/or a higher temperature will be
required to carry out the dissolution at this point. If the
solvents are different, the volume and temperature of dissolution
are so chosen to provide a pitch of the proper softening range and
physical characteristics. For example, if benzene is used as a
solvent, a solvent-pitch ratio of 4:1 (V/W) is appropriate for the
first extraction at room temperature, and a solvent-pitch ratio of
50:1 (V/W) at reflux temperature is useful for the second
extraction to provide a final product having a softening range of
240.degree.-260.degree. C. from a 150.degree. C. softening point
starting pitch. The same effect can be accomplished by using a
benzene solvent in 5:1 solvent-pitch ratio and a quinoline solvent
in 10:1 solvent pitch ratio for the two extractive steps.
The next step in the purification process is the separation of the
second-phase insoluble material, commonly called quinoline
insolubles, from the pitch-solvent mixture. This separation is
carried out by filtration, centrifugation, or similar separation
technique.
The filtrate is then stripped of the solvent. The stripping
operation is preferably carried out at less than atmospheric
pressure in order to avoid heating the pitch to a temperature at
which rearrangement and cracking can occur. Thus, for example a
quinoline-pitch (10:1) mixture is heated for about 8.5 hours,
ultimately attaining a temperature of 235.degree. C. at 0.15 mm.
(in.) in order to completely remove the quinoline therefrom.
Solvents useful for the dissolution steps of this invention include
acetone, benzene, toluene, o, m, p-xylene, Tetralin, methyl ethyl
ketone, quinoline, isoquinoline, indole, pyridine, quinoxaline,
pyridine, pyrimidine, pyrazine, .alpha.-, and
.beta.-methylnaphthylene, dimethyl formamide, dimethyl acetamide,
dimethylsulfoxide, dimethylsulfone, and the like, and mixtures
thereof in appropriate concentrations to carry out the manipulative
steps as required by this invention.
A more complete understanding of the process of this invention can
be obtained by reference to the following examples which are
illustrative only and not meant to limit the scope thereof which is
fully expressed in the hereinafter appended claims.
EXAMPLE 1
A coal tar pitch with a softening point of about 187.degree. C.
(ring and ball - A.S.T.M. D-36) is ground to -100 mesh size. Four
hundred grams of this pitch is triturated with 2 liters of benzene
at room temperature for 10 minutes.
The suspension is filtered, and the filter cake washed with 300 ml.
of hexane and dried in vacuo for 4 hours. A residue of 294 g. is
obtained which is mixed with 2,940 g. of quinoline for 10 minutes
at 60.degree.-70.degree.C. The suspension is filtered using 25 g.
of diatomaceous earth as a filter aid.
The filter cake is washed with 400 ml. of quinoline and the
quinoline is added to the previous filtrate. The combined filtrates
are evaporated in vacuo to yield 195 g. of a pitch suitable for
melt spinning. Softening point: 270.degree.-280.degree.C.
EXAMPLE 2
A coal tar pitch of similar origin to that of Example 1 (10 g.) is
extracted by stirring with 100 ml. of quinoline at about room
temperature for one hour. The mixture is filtered and the residue
washed well with 10 ml. of quinoline. The filtrates are combined
and the solvent removed therefrom by evaporation in vacuum.
The resulting residue is ground to -100 mesh and extracted by
stirring into 4 volumes (W/V) of a mixture of benzenehexane
(3:1).
The solvent is removed and the residue dried in a vacuum oven for
four hours to yield a spinnable pitch. Softening point:
210.degree.-240.degree.C.
EXAMPLE 3
A polyvinyl chloride pitch of softening point
150.degree.-160.degree. C. is milled to -100 mesh and the resulting
powder is extracted with 4 volumes (W/V) of a 10:1 (V/V) mixture of
acetone-benzene at the freezing point of the solvent mixture. After
stirring the mixture for one hour, the pitch is separated by
decantation and the residue dried in vacuo. A second solvent
mixture comprising pyridine-benzene, 20:1 (V/V) is added to the
solid pitch powder. The mixture is refluxed for 12 hours and then
filtered. The filtrate is evaporated to dryness resulting in a
spinnable pitch of softening point over 250.degree. C.
EXAMPLE 4
A 52.degree. API light crude naphtha was subjected to catalytic
cracking at high pressure in the presence of steam to produce
ethylene, other low boiling gases and a resinous residue having the
following properties:
Softening point (Ring and Ball), .degree. C. 45 Specific gravity
(at 15.degree.C.) 1.180 Conradson carbon percent 36.5 Ash do 0.02
Sulfur do .38 Benzene soluble do 98.0
This residue has a dark brown-black color and a glossy resinlike
appearance. In an ASTM (D-20) distillation, 44 percent by weight of
the material distilled. An analysis of the overhead showed it to be
a highly aromatic material containing substantial amounts of
phenanthrene, anthracene, fluorene and various derivatives of these
cyclic compounds.
A 100 g. lot of this resin is dissolved in 4 liters of quinoline
and filtered through a pre-coat of 25 g. of activated carbon filter
aid at 100.degree. C. in a steam jacketed fine porosity metal
filter. The quinoline is removed in vacuo. The resulting pitch is
mixed with an equal volume of benzene and stirred in an indented
flask at the reflux temperature of benzene for 4 hours. The pitch
layer is separated by decantation of the benzene layer. A vacuum is
pulled on the flask for about 1 hour to remove the last traces of
benzene and the pitch is ready for melt spinning.
EXAMPLE 5
A gas-oil fraction is separated from the straight thermal
distillation of a mid-Continent crude oil and is catalytically
cracked in the presence of a zeolite catalyst at about 500.degree.
C. with the separation of gas and gasoline. A side stream of
substantially the same boiling range as the gas-oil charging stock
is separated and conducted into a second catalytic cracking zone.
The side stream of cycle oil therefrom is heated to a temperature
of 525.degree. C. in a thermal cracking unit maintained at about
400 psi. The vapors are stripped and recovered for gas and gasoline
and the high boiling aromatic cut having the following
characteristics is used as starting material.
A.P.I. gravity -20 Distillation range <235.degree. C. none
<270.degree. C. 16% < 315.degree. C. 34% <355.degree. C.
44% Residue 56%
The above-defined starting material, 100 g. is triturated with 2.5
liters of a mixture of benzene-quinoline, 100:1 (V/V), at about
5.degree. C. for 20 minutes. The pitch is separated by decantation
of the benzene-quinoline solvent. The pitch is ground to -100 mesh
and then added to another benzene-quinoline mixture, 2.5 liters of
a 1:50 (V/V) solution at ambient room temperature. The solvent
effects essentially complete solution. The solid particles are
collected therefrom by adsorption on charcoal and centrifugation of
the solids.
The solution is then evaporated to dryness to provide a spinnable
pitch.
* * * * *