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Патент USA US2119213

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‘2,119,213:
Patented May 31, 1938
‘PATIENT OFFICE
UNITED STATE S
2,119,213
HIGH MOLE CULAR
WEIGHT PHENOLIG SUBSTANCES FROM
COAL
PRODUCTION --
OF
‘Leo Kasehagen, Pittsburgh, Pa., assignor to Car
negie Institute of Technology of Pittsburgh,
Pa., Pittsburgh, Pa., a corporation of Penn
sylvania
No Drawing. Application May 13, 1937,
Serial No. 142,429
16 Claims. (Cl. 260-153)
The change in composition of phenolic material
My invention relates‘to the treatment of coal
with change in the temperature of the treatment
is shown in the following table. All treatments
whereby there is produced a highv molecular
Weight phenolic substance. I have found that
were made with 5 N NaOH:
‘ valuable products, phenolic in nature, are ob
15 tained by ‘heating coal, preferably crushed to .16
to 20 mesh (Tyler standard screen scale) with an
aqueous solution of an alkali metal hydroxide at
a suitable temperature in a closed pressure vessel
Temper-
ature
lined with a suitable material, such, for example,
1
Both the amount of the phenolic material
formed and its composition depend upon the tem
15 perature at which the treatment takes place and
the concentration of the solution used during
_
S
l. 53
O in OH
0
groups
0.92
14. 61
77.52
5. 35
1.32
1.21
14. 42 __________ -
80.04
< 5. 30
l. 53,
1. 16
11.97
__________ __
80. 98
5. 44
1. 55
0. 64
11.39 .......... __
110
7. 08
centage as the temperature is raisedand, based
on yields of the material in percentage of the dry,
ash-free coal, as set forth in the ?rst table above,
it has been found that the optimum temperature
of treatment is in the neighborhood of 300° to 20
350° C.
‘
I have also found that the most effective
period of treatment need not exceed approximate~
1y 5 hours. The following table gives the rates of
production of phenolic substances when 50 grams
in which the yields of the phenols are calculated
on a dry, ash-free basis, illustrates the trend of
yields with variations in the temperature of treat
ment.
EEG-gym,
treatment
5. 35
N
From this table, it is apparent that there is an
hydroxide or potassium hydroxide is used, but‘
the amounts are appreciable only at temperatures
ranging from 275 to 350° C. The following table,
30
H
increased carbon and a decreased oxygen per
the alkali treatment. In the case of Edenborn
coal, some material of phenolic nature is formed
at all temperatures in the range from 250 to 400°
20 Cl'when an alkali metal hydroxide such as sodium
2
C
77. 59
10 as nickel or silver, which will resist the action
of the hot alkali. The phenolic substances are
found in the, solution.
I
of Edenborn coal are treated with 5 N sodium
hydroxide at about 325° C.:
-
Yield percent of
?'fgglign
dry, ash~iree .
coal (using
NaOH_5N)
hours
%
2%
5%
Rate of produc
tion of phenolic
30
substances in
grams per hour
1.58
0.72
0.16
35
This table shows that the reaction starts at
high velocity, but decreasesin velocity rapidly
with the passage of time so that the reaction is
40
esentially complete at the end of approximately 40
The effect of changing the concentration of the
alkali solutionon the yield of the phenolic material
is shown in the following table. The tempera
5 hours. It has also been observed that certain
phenolic substances can be produced by merely
heating to a reaction temperature and allowing
ture in each case was 350° C. and, the alkali used
was sodium hydroxide:
Alkali con- '
Percent yield of
centration
phenolic material
0. 1 N__ __
5.0 N__
l0. 0 N._ __
l5.0N__._
vessel in which the reaction was carried out along
with the alkali solution. , The salts may be pre
6. 9
1. 3
cipitated from the alkali solution by neutralizing
with acid or by saturating with carbon dioxide,
the latter methodiindicating that the material is
phenolic rather than acidic. An additional in
0.8,
60. 0 %l_ _
i
treatment when sodium hydroxide is used as the
alkali is in the form of soluble sodium salts of
the phenols and these salts are removed from the
11. 0
,
1. 2
80. O %_V_-
0. 8
100.0 %__
0.7
The above tables show that a temperature of
the order of‘ 275-350“ C‘. is the optimum tempera
ture of treatment for Edenborn coal and the
optimum alkali concentration ranges from about
0.1 to 5 N.
'
7
50
dication of the phenolic nature of the material 55
is afforded by the fact that methylation, which
55
60
~‘
The phenolic material produced by the alkali , ~
l. 2
1. 0 N.-__
50
to/ cool.
maybe brought1about‘ by either dimethyl sul
phate or diazomethane, results in a product which
cannot be hydrolyzed by the use of a boiling
,
alkali solution.
l
60
2
2,119,213
The high ,molecular weights of the phenolic
production of _ high molecular‘ weight phenolic
material are indicated by the fact that they are
substances, the steps comprising heating the coal
amorphous solids, cannot be distilled without de
,with an aqueous solution ranging from about
composition even in a vacuum, and are completely
0.1 N to 99% of an alkali metal hydroxide, and
insoluble in the common organic solvents, with precipitating the substances from the solution.
the exception of methanol and acetone, in which
8. In the treatment of bituminous coal for the
they are only slightly soluble. So far as I know, production of high molecular weight phenolic
fused catechol is the only organic solvent in which substances, the steps comprising heating the coal
they dissolve completely. Apparent molecular with an aqueous solution ranging from about
10 weights determined cryoscopically in this solvent
0.1 N to 99% of sodium hydroxide, and precipi 10
range from 218 to 242 but the physical qualities tating the substances from the solution.
are not at all consistent with such low molecular
9. In the treatment of bituminous coal for the
weights so that these ?gures undoubtedly repre
production of high molecular weight phenolic
sent the size of the building unit of the phenol substances, the steps comprising heating the coal
16 rather than the size of'the phenol molecule as
with an aqueous solution ranging from about 15
it exists in the solid state. Equivalent weights
0.1 N to 99% of potassium hydroxide, and'pre
obtained by methylation and determination of
methoxyl content were of the same order of mag
nitude as the molecular weights determined in
20 catechol.
It is not feasible to set forth all the conditions
necessary for the formation of the phenolic prod
ucts from all coals, but the optimum conditions
can readily be determined experimentally for any
25 coal by' following the teachings of this invention.
While I have described the preferred form of
my invention, it is to be understood that various
and 400° C. with an aqueous solution ranging
from about 0.1 N to 99% of an alkali metal hy
droxide, and precipitating the substances from
the solution.
'
'
'
11. In the treatment of bituminous coal for the
production of high molecular weight phenolic
substances, the steps comprising heating the coal
without departing from the spirit of the inven~
at a temperature between approximately 250° C.
the appended claims.
I claim:
production of high molecular weight phenolic
substances, the steps comprising heating the
coal with an aqueous solution of an alkali metal
hydroxide, and precipitating the substances from
the solution.
and 400° C. with an aqueous solution ranging
from about 0.1 N to 99% of sodium hydroxide,
and precipitating the substances from the solu
.
1. In the treatment of bituminous coal for the
tion.
12. In the'treatment of bituminous coal for the
production‘ of high molecular weight phenolic
substances, the steps comprising heatingthe coal
at a temperature between approximately 250° C.
and 400° C. with an aqueous solution ranging
.
2. In the treatment of bituminous coal for the
40
production of high molecular weight phenolic
substances, the steps comprising heating the coal
at a temperature between approximately 250° C.
modi?cations in the details thereof maybe made,
30 tion, which is not to be limited other than as in
35
cipita'ting the'substance's from the solution.
10. In the treatment of bituminous coal for the
production of high molecular weight phenolic
substances, the steps comprising heating the coal
from about 0.1 N to 99% of potassium hydroxide,
and precipitating the substances from the solu
tion.
'
'
1
-
'
with an aqueous solution of sodium hydroxide,
13. In the treatment of bituminous coal for’the
and precipitating the substances from the solu
tion.
3. In the treatment ofbituminous coal for the
production of high molecularv weight phenolic
substances, the steps. comprising heating the coal
with an aqueous solution of potassium hydroxide,
at a temperature between approximately 250° C.
and 400° C. with an aqueous solution ranging
from about 0.1 N to 99% of an alkali metal hy
droxide for a period up to about 6 hours, and pre
and precipitating the ‘substances from the solu
cipitating the substances from the solution.
production of high molecular weight phenolic
substances, the steps comprising heating the coal
tion.
4. In the treatment of bituminous coal for the
production of high molecular weight phenolic
substances, the steps comprising heating the coal
at a temperature between 250° C. and 400° C.
55 with an aqueous solution of an alkali metal hy
14. In the treatment of bituminous coal for the 50.
production of high molecular weight phenolic
substances, the steps comprising heating the coal
at a temperature between approximately 275°
and 350° C. with an aqueous solution ranging
from about 0.1 N to 5 N of an alkali metal hy- I
droxide, and precipitating the substances from
droxide, and precipitating the substances from
the solution.
the solution.
a
5. In the treatment of bituminous coal for the
production of high molecular weight phenolic
substances, the steps comprising heating the coal
at a temperature between 250° C. and 400° C.
with an aqueous solution of sodium hydroxide,
and precipitating the substances from the solu—
tion.
‘
6. In‘ the‘ treatment of bituminous coal for the
production of high molecular weight phenolic
substances, the steps comprising heating the coal
at a temperature between 250° C. and 400° C.
with an aqueous solution of potassium hydroxide,
70 and precipitating the substances from the solu
tion.
7. In the treatment of bituminous coal for the
40.
‘
-
'
15. A high. molecular weight phenolic sub
stance which is obtained by treating bituminous
coal at a temperature between 250° and 400° C.
with an aqueous solution ranging from about
0.1 N to 99% of an alkali metal hydroxide.
16. A phenolic substance having apparent mo
lecular weights ranging from 218 to 242 and
whose actual molecular weights are a multiple 05
of the apparent molecular weights, which is obe
tained by treating bituminous coal at a tem
perature between 250° and 400° C. with an aque
ous solution ranging from about 0.1 N to 99%
of an alkali metal hydroxide.
70
‘LEO KASEI-IAGEN.
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