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Патент USA US2085500

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Patented June 29, ‘ 1937
~ 2,085,500 ‘;
‘Joseph Hidy James. Pittsburgh, Pa, assignor to
'‘ Clarence P. Byrnes, trustee, Sewickley, Pa.
No Drawing.
Application March 26, 1924,
Serial No. 702,136
16 Claims.
In various copending applications, including my
application Serial No. 435,355, ?led January 6,
1921, I have disclosed partial oxidation processes
for the treatment of mineral oils, including pe
troleum, shale oil and theoil or tar produced by
thelow temperature distillation of coal. In such
(Cl. 260-9912)
oil charged. The speci?c gravity of
densed product was .892 at 60’ F.
con- ’
The Engler distillation on the oxidation prod-.
'uct mixture showed the following:
Per cent I
by volume
method,‘ the oil‘ or fraction thereof is vaporized,
mixed ‘with air, and the mixture passed at a
Under 200° C
200 to 250° C..
regulated temperature below a red heat in con-'
tact with ‘a catalyst, such. as ‘the oxides or com
' 250 to 300° C-
' 300 to 350° C _________ -_~ ____ __' ______ _.».____
pounds of molybdenum, vanadium, ‘etc. The con
densedproducts of this partial oxidation process
350 to 400° C..
20 m
extend from-alcohols through‘aldehydes, to alde
hyde fatty acids, all of varying molecular weights,
' Thisproduct was then subjected to a vacuum
steam distillation carried-out on several liters u
of the product, the various cuts being taken at
My present invention relates to the treatment approximately the volumes above shown. In the
of such mixturescontaining oxygen derivatives further description, I shall refer to each of the
depending upon‘ the fraction employed for the
of hydrocarbons in which aliphatic hydrocarbons portions by its atmospheric pressure distillation
20 predominate, in the range from alcohols to acids range, it being understood that the particular :0
which, according to the present invention, I frac fraction discussed was not separated by atmos
pheric pressure distillation, but that a cut corre
to this distillation was made by taking‘
into separate fractions.‘ I have found that where‘ sponding
volume in the vacuum steam
careful fractionation is employed, there is a gra
dation in properties‘ of both the saponi?able' and , distillation.
non-saponi?able portions of each fraction of the
Procedure with the “under 200° C’. fraction”
. _
product treated, in passing from the fraction of
(method A)
lowest average molecularv weight to that of high
This portion was boiled under an inverted con
est average molecular weight, which it is possible
30 to vaporize underpthe best distillation means. denser with a‘ 20% solution of caustic soda for 80'
Steam is preferably employed in connection with seven hours. The volume offraction taken was
‘500 cc. and the volume of 20% caustic was 100 cc.
‘ tionally distill preferably by‘ a vacuum process
this vacuum distillation, as'it'aids in vaporiza- ' On cooling, a solid cake of soap separated, this
tion and also serves to hydrolize the wax-like being a mixture of sodium soaps of the resinifled
bodies and anhydrides that are present.. The _ aldehyde acids of this fraction. These resin acids 86
vacuum distillation was employed in order to
were then liberated from the soap by adding a '
‘vaporize each fraction at the lowest possible
temperature, thus causing the least possible ‘for
slight excess of dilute sulphuric acid. The resin
‘acids thus liberated were of ,a brick- red color,
mation of decomposition’ products. Each such , completely soluble in alcohol and in benzol, and
without further purification, showed a softening
40 fraction of the product contains a material per
centage of oxygen derivatives other than acids point of 175° C. and were completely melted at
and in the range from alcohols up to acids.
The following are examples of ‘treatments of
the ‘product-~mixture from the ‘main oxidation
process, the‘ raw material ofwhich' was a mix
ture of 75% Pennsylvania petroleum refinery wax
distillate (untreated) and 25% of ordinary‘Penm
sylvania petroleum gas oil. Such oils are mainly
aliphatic. The condensed oily oxidation product
mixture was‘ about 85% by volume of the raw
210° C.
Withth’e resins of this and of all other frac
tions, I discovered that if they are washed with
certain solvents; such as petroleum, ether or gas-I 45
woline, I can wash out a small amount of oil and .
softer acids, thus raising both the softening and
the melting points of the resins and also improv
ing the colors-of the remaining resin acids. This
is'an important feature of my invention, as it 50
may be applied to any and all such resins and will
greatly improve them, both by raising the melt
bustion is clean and complete, leaving no carbon
or tarry matters; whereas the ordinary kerosene
hydrocarbon mixture in the same boiling range
ing point and improving them in color.
The non-saponi?able portion of this fraction is produces sooting and clogging under the same
amenable to the ordinary decoloring and deodor ' draft and' gravity burner conditions. This frac
izing processes known to industrial chemists. For
example,v when this portion or fraction is sub
tion may be used alone as a furnace oil or it may
in color and has a pleasant ethereal odor. This
‘product is suitable for a solvent, for motor fuel,
and sooting thereof under burner conditions.
Where this non-saponi?able fraction is not
usedras a furnace oil, it may be readily handled
by returning it to the oxidizing apparatus, either
alone or mixed with fresh oil. Where this is 15
done, I have found that the partially oxidized oil
is always attacked and oxidizes more readily than
be blended with ordinary hydrocarbons of‘ either
jected to the ordinary sulphuric acid and caustic the same range or even of higher'boiling range,
‘soda agitations and to subsequent re-distillation, .since it acts as a kindling oil for the ordinary
10 a product is obtained which is almost water white hydrocarbon and greatly minimizes the smoking 10
or for a thinner or turpentine substitute in'the
paint and varnish industry.
In certain cases in the latter industry, the puri
?cation treatment need not be resorted to, as
there is sufficient concentration of aldehydes, ke
tones and ethers in this fraction to; make it of ' fresh oil when subjected to the air-vapor catalytic
great value as a thinner where aslight color is oxidation. If it is desired to isolate the alde
not objectionable.
hydes and ketones in this fraction, the saponi? 20
cation and separation of the acids should be car
Procedure with the “under 200° C’. fraction”
ried out with calcium hydroxide, as above noted
(method B)
under procedure “B” for the ?rst fraction, fol
This method may be applied to the ?rst frac
25 tion where it is desired to obtain either the alde
lowed by bisulphite treatment.
The calcium soaps may, if desired, be decom
hyde acids or the aldehydes in as high a state
of purity as possible. In this case, instead of
of alcohol to make esters in a manner similar to
saponifying with caustic soda, I employ calcium
that above noted under the ?rst fraction.
hydroxide, as I have found that this reagent
30 brings about very slight resini?cation of the
aldehydic substances. In this procedure the frac
posed by a suitablemineral acid in the presence
Procedure with the'250 to 300° C’. fraction
This fraction wil1,‘in general, be handled the
tion is boiled under an invert condenser with an - same as the 200' to 250° C. out, but the resin
acids will have lower melting points and the non
saponi?able oil will have a higher boiling range.
v35 tion and one volume of the lime water solution . The untreated resin acids should soften in the 35
and adding more of the lime solution as the neighborhood of 145° C. The removal of alde
reaction proceeds._
hydes and ketones should in this case preferably
, The calcium soaps may then be decomposed be preceded by calcium hydroxide treatment, as
by a suitable mineral acid in the presence of before noted.
alcohol, to form esters of the organic ‘acids pres
Procedure with the 300 to 350° fraction
ent; or the liberated acids may now be resini
?ed caustic soda by a treatment similar to
that above recited under “A" process.
This method is carried out the same as 'in the
Bythe lime saponi?cation, a product of a good preceding groups, and the resin acids will have
color is obtained from a non-saponi?able layer still lower melting points. For example, with 45
the wax distillate gas oil product which I have
without further treatment. This method is par
ticularly applicable where it is desired to isolate described, resin acids were obtained from this
the aldehydes for any purpose. All that is neces-. out which, when untreated, softened at 132° C.
sary is to agitate the non-saponi?able layer with and were completely melted at 138° C.- These
excess . of calcium hydroxide solution, starting
.with ?ve volumes of the oxidation product frac
a saturated or nearly saturated solution of sodium resins were diss'olved almost completely (95%)
bisulphite, later removing and decomposing the 'in alcohol and were completely dissolved in ben
aldehyde-bisulphite compound. Any ketones vzol.
present are removed along with the aldehydes.
the 300 to 350° 0. fraction
The non-aldehydic portion will .contain many
(method B)
55 oxidation derivatives, such as alcohols, ethers
andpossibly “bridge” oxygen derivatives of the
original hydrocarbons.
Procedure with the 200 to 250‘?
(method A)
combinations with calcium hydroxide, using the
preceding “A” treatment with no further treat
ment, a mixture of ‘ resin acids which softened
at 160° C. and became completely fused at 175° C.
was obtained. These resins are easily soluble in
resulting calcium soaps in grease manufacture.
The non-saponi?able oil may be returned to the
, oxidizer or'may be used for lubrication where a 60
' When the saponi?cation is carried out as in the
alcoholv and in benzol. .
In this method, I saponify the acids and their
The non-saponifiable 011' here obtained can not
be put to anyv of the uses referred to in the
thin oil is desired.
Procedure with the 300 to 350° c. fraction
(method 0)
This method involves the sulphonation of the 65
total 300 to 350° C. out. I prefer to carry out this
sulphonatlon as follows: 5 volumes of the oxidized
oil of this out are treated with one volume of
“A" method of the preceding fraction, because fuming sulphuric acid (approximately lilZoleum)
of its higher boiling range. This non-'saponi?able .by dropping the acid slowly into vthe oil with
' oil ‘may, after the removal of ‘the acids, be utilized
.violent agitation, keeping the témpe'ratureb'elow
as a “furnace” oil, and is of special advantage in , 50° C. and continuing the agitation for three
gravity feed burners. ,On account of its contain
ing oxygen compounds,‘ this material is readily
Tests have shown that the com
- 78. ‘combustible.
hours after all of the acid'is added; When the
reaction mixture is allowed tostand for'from 48
to 72 hours, the excess sulphuric acid,‘.together
with water and a considerable quantity of the
__sulphonated organic product, settles to the bot
tom}, The “top oil” layer here contains the sul
phonated and other acids that are soluble in the
oil. It is better to draw this off carefully from
the sulphuric layer below and saponify by agita
J tion with hot causticsoda or sodium carbonate
temperature and pressure, this being the mixture
obtained at condensers in the ordinary operation
of the catalytic vapor-phase oxidation.
' Procedure with scrubber product
There is, however, another product which also
consists of a mixture of oxidation compounds and
which does not‘ ordinarily condense with the
' solution. If a solubleoil is desired, it is possible
‘ by careful addition of alkali to saponify the sul-. .‘ products above noted, but is .usually carried on
10 phonated and other acids and leave a su?lcient ' . past the condensers with the eiliuent gas stream. 10
amount of soda soap in the oil to completely
emulsify it when water is added. A good plan
here is to saponify to this point by heating the
oil with dry caustic soda when the greater part
of the soap remains in solution in the oil.
Instead of saponifying the acids in the “top"
oil by caustic soda or sodium carbonate,-as above,
I may use calcium hydroxide and’ thus convert
If a scrubbing system be installed in series with
the condensers and the scrubbing liquid consist of '
linfe water or a solution of, say, ‘soda ash, I can
‘almost completely-remove these low molecular
weight bodies from the gas vapor e?‘luent. I have
found these particular bodies to be most active
toward the resini?cation reaction, of any of the
acids formed in the catalytic oxidation process.‘
Because of this fact, it is preferable in most cases‘
I may saponify with caustic soda or sodium car
.to use lime ‘water in the scrubbing system, as this
bonate as above and remove the soda soaps by ' is the mildest cheap alkali available. Even on
repeated washings, utilizing the separated soaps warming the‘ solution of these calcium soaps
as cheap detergents.
(since these calcium soaps are more soluble in
the whole top oil layer intoa grease. '
The "sulphuric” layer above referred to is’
treated with sodium chloride or sulphate to “salt
out” the organic acids. This process is repeated
on the ‘water emulsion of the sulphonated‘acids
until the layer of organic acids is obtained free
‘from sulphuric acid. This also consists almost
30 completely of saponi'?able matter (sulphonated
acids, oxygenated acids and ordinary fatty acids)_
water than those from any of the preceding
oxidation products described) calcium resinates
are obtained which become darker brown as the
heating continues. The color of the resin acids
liberated and the degree'of resini?cation depend
on the time during which the alkali or alkaline
earth metal soaps are heated in contact with the ‘
_ free alkali or the free alkaline earth metal hy
and is amenable to easy saponi?cation in the > droxide. Where sodium carbonate or caustic soda
usual way by caustic soda or carbonate of soda. is the alkali used in the scrubbing solution, the
There is thus produced a very good soap .that resini?cation may be carried to thelpoint of mak-‘
.35 can be utilized in the-coarser kinds of cleaning.
ing brown‘ resins that are infusible and insoluble '
1 It froths readily and emulsifies oils more readily _in any of the ordinary solvents, such ‘as alcohol,
than do the ordinary commercial soaps.
ben‘z'ol, etc. .
»Where these soaps are in solution, I may
Procedure with 350'to 400° 0. fraction (method A) ,
This method is that of isolating the resin vacids
as outlined for the preceding fractions. Here,
‘ _ however, this is usually not advisable, as the
resins from the foregoing wax distillate gas‘ oil
‘ oxidation mixture were darker in color than those
from the lighter fractions and showed a soften
ing point of 62° C. andv were completely melted at
66° C. Their solubility ‘was almost identical with
that of the resins from the preceding fraction.
Procedure with 350°, to 400° 0. fraction.’
(method B)
There is present in this fraction an'oxldation
mixture of su?iciently high average molecular
weight to show in the acids the characteristics of‘
65 the ordinary commercial fatty acids. Hence, for
example, by saponifying with calcium hydroxide,
that is, by agitating the total fraction with cal
cium hydroxide solution, we can make a lime
soap grease in one operation as it is not neces
60 sary to make- a separation of the acids from the
oil in this case.
Procedure with 350“ to 400°‘ 0. fraction'
, (method 0)
This method relates to the sulphonation ‘of the
fraction and is carried out in a manner almost
bleach them by treating the solution with a
stream of chlorine gas. Passage of the gas may 40
be continued until enough acid has been formed
to liberate the bleached resin acids. I have also -
found that if dilute sulphuric acid be used to
liberate the acids already resini?ed, chlorine may
be used on the remaining acids in solution to
resinify and ?nally precipitate the bleached resin
acids formed.
Washing method of acid separation
In addition to the foregoing procedures for
the separation of the ‘resin acids of the various
fractions,» it isv possible witheach fraction to
separate these acids into two or more groups,
each group having different properties, by the
selective action of certain solvents.
For ex
ample, as noted in the description of the products
of. the ?rst fraction, I have found that if the
resins of a certain fraction be agitatedv with pe
troleum ether, or gasoline, two groups of acids
are ‘obtained, one group being insoluble in pe 60
troleum ‘ether or gasoline and having a much
higher melting point than the ‘original mixture
of resins, and of course, a much higher melting
point than the portion‘ soluble in petroleum ether.
or gasoline.~ I have found after much experi
mentation. that the application of the gasoline
wash raises the melting point of theeresins of a
identical with that outlined for the third method
of the preceding fraction. Here again it should certain fraction ‘which are not soluble in the
be noted that the high average molecular weight H wash by from 20 to 30 or even 50° C. It is re
of the acids and the non-saponiiiable oil imparts
70 to the oxidation mixture the characteristics of the ' markable, that even comparatively small portions
of ' the gasoline-soluble acids will cause the melt
ordinary fatty acids and fatty oils.
ving point to fall below 100° C. Amounts as low
‘ In all the foregoing outlines, I have considered as 5% of the gasoline-soluble acids will keep the
~ those oxidation products of hydrocarbons which melting point too low for many purposes, and
were condensable under ordinary conditions of
yet the simple washing method above described 75
_ will result in a yield‘ of from 90 tov95% of a resin
mixture melting from 20° C. to 30° C. higheia,
By treating any of. the above resini?ed products
from the oil fractions, preferably while in the
form of their soluble soaps, (usually sodium or.
potassium . soaps), with chlorine in the water
solution, bleached resins of ?ne appearance can
be obtained. Usually such resins, like practically
all those above ‘described, are soluble in‘ alcohol
10 or in benzol or in mixtures of these two solvents.
In all my processes of ' resini?cation, the prop
erty of the product obtained was determined by
Where it is desired to improve certain physical
properties of the resin acids, such as toughness
and elasticity, I can accomplish this by taking
any of the foregoing resin acids vand forming
their glycerine esters. This is usually carried out
by heating the resin acid mixture with an ex
cess of glycerine, ‘usually aiding the esteri?cation
by the addition of a small percentage of sulphuric 10
acid or by passing a stream of dry hydrochloric
acid gas through the heated solution. After the
esteri?cation is complete, the excess glycerine is
to be the main ones:
easily recovered by adding water to the cooled
reaction mixture and the esteri?ed resin acids 15
?ltered oil and washed.
' (2) The particular fraction of the product
from which the resins have been separated;
(3) The method of resini?cation. This is de
scribed in my copending application Serial No.
520,715, for the renewal of. application Serial No.
395,942, ?led July 13,‘ 1920 and‘ also in this ap
plication. Generally speaking, the milder the
alkalilused, the less will be the resini?cation.
For example, it is possible in the case of the cal
cium soaps of low molecular weight acids to ob
tain suilicient resini?cation by the use of lime
only, while if these acids be liberated from the
calcium and be further resini?ed by caustic soda
solution, I ‘obtain resins practically ,infusible
and insoluble. A convenient method of separat
ing and resinifying the acids of a given reaction
mixture is to carry out the saponi?cation with a
35 mixture of sodium carbonate and calcium hy
droxide (slaked lime). I prefer to keep the cal
cium hydroxide in excess, for example, I may use
from 8 to 10. grams molecular weights of calcium
hydroxide to one g. mol. of sodium carbonate.
4,0 This enables me to utilize the action of a dilute
solution of‘ caustic soda in saponi?cation and to
continuously remove the soaps formed, asin
soluble calcium soaps. The removal of these
soaps from the sphere of the reaction hastens
the saponi?cation of the remaining acids and
‘acid compounds and anhydrides present in the
reaction mixture.
Such a mixture may also be used as a scrubbing
I liquid to aid in the further recovery of- the vola
tile oxidized'acids from the gas vapor stream be
Yond the condenser.
(4) The degree of oxidation to which a. given
mixture is subjected. In general, this works to
ward the higher petroleum ether insoluble resins,
55 where the oxidation has been more vigorous.
, These resins are of higher melting point in a
given fraction and more di?icultly soluble than
the petroleum-ether soluble acids. Where the
oxidation has been vigorous, the concentration of
caustic used in saponi?cation and resini?cation
becomes of minor importance. In addition
where color is an important factor in the resin
produced,- I may bleach the product by taking
the water solution of the sodium resinates and
65 passing chlorine gas into the solution or by treat
ing the solution with a solution of sodium hy
pochloride. Where chlorine is used, Imay pro
ceed with the chlorine treatment until hydro
tion of bleaching powder may also be used. .
several factors, of which I believe the following
(1) Chemical character of the hydrocarbons
originally subjected to the air-vapor-catalytic
original fraction or the sodium soap with a solu
chloric acid is formed in su?icient amount to
liberate the bleached resin acids, without further
mineral acid treatment. I may also pass chlo
rine into a suspension of the calcium resins,
although this method is not as eifective as the
sodium method above. Treating either the
I claim:
1. In the treatment of partial oxidation prod
ucts in the range from alcohols to organic acids
and containing hydrocarbon derivatives other 20
than acids, the steps consisting of separating from
the same a plurality of fractions, each containing
a material percentage of derivatives other than
acids, and chemically treating at least one of said
2. In the treatment of a liquid partial oxida
tion product in the range from alcohols to organic
acids and containing hydrocarbon derivatives
other than acids, the steps consisting of separat
ing from the same a fraction by distillation con
taining a material percentage of aliphatic derive
atives other than acids, then converting a portion
of said fraction into resin acids and removing
impurities from said acids.
‘3. In the treatment of a liquid ‘partial oxida 35
tion product in the range from alcohols to organic
acids and containing hydrocarbon derivatives
other than acids, the steps consisting of separat
ing from the same a fraction by distillation con
taining a material percentage of aliphatic deriv 40
atives other than acids, and then saponifying a
portion of said fraction, separating the saponi?ed
from the unsaponi?ed portion of said fraction,
and bleaching the. saponi?ed portion.
4. In the\treatment of a liquid partial oxida 45
tion product in the range from alcohols to organic
acids and containing hydrocarbon derivatives
other than acids, the steps consisting of separat
ing from the samea fraction by distillation con
taining a material percentage of aliphatic deriv
atives other than acids, then saponifying a portion
of said fraction with lime, and separating the
saponi?ed from the unsaponi?ed
portion of said ' ‘
5. In the treatment of a liquid partial oxida
tion product in the range from alcohols to organic
acids and containing hydrocarbon derivatives
other than acids, the steps consisting of separat
ing from the same afraction by distillation con
taining a material percentage of aliphatic deriv 60
atlves other than acids, then saponifying a portion
of said, fraction with soda and lime, and separat
ing the saponi?ed from the unsaponi?ed portion
of said fraction.
6. In the treatment of partial oxidation prod
ucts of hydrocarbons, the steps consisting of resin
iiying at least a portion thereof, and then washing
out of said resini?ed material the lower-melting
point portions thereof.
7. In the treatment of liquid partial oxidation
mixtures in the range from alcohols to aldehyde
fatty acids, the steps consisting of vacuum dis
tilling the same into fractions of diiferent average
molecular weight, and then chemically treating
at least one of the fractions to form chemical 75
compounds of portions of said fractions, and hydrocarbons predominate containing alcohols
and having a boiling point above 300° C., the step
separating said compounds.
8. In the treatment of liquid partial oxidation
mixtures in the range from alcohols to aldehyde‘
5v fatty acids. the steps consisting of steam vacuum
distilling the same into fractions of di?erent
average molecular weight, and then chemically
treating at least one of the fractions to form
chemical compounds of portions of said fractions,
10 and separating said compounds.
consisting of sulphonating the same.
12. In the treatment of a mixture of oxygen
derivatives of hydrocarbons in which aliphatic
hydrocarbons ‘predominate containing alcohols
and having a‘boiling point above‘ 300° C., the step
consisting of sulphonating. the same and then
13. As a new composition of matter, a mixture 10
of sulphonated oxygen derivatives of hydrocar
9. I In the treatment of a. partial oxidation prod
not having hydrocarbons which already contain
arti?cially-introduced chemically-combined oxy
gen to di?erent degrees of oxidation,v and which
15 contain like bodies of different molecular weights,
bons in which aliphatic hydrocarbons predomi
nate having a boiling point above 300° C.
14;. As a new composition of matter, a detergent
containing essentially a sulfonated and saponi?cd
‘the steps consisting of fractionating the same ' mixture of oxygen derivatives of hydrocarbons in
into liquid fractions of different average molec
which aliphatic hydrocarbons predominate hav
ular weights and treating the lighter fractions
ing a boiling point above 300° C.,
15.v As a new composition of matter, a sulphoé
nated and saponi?ed fraction of a mixture of 20
oxygen derivatives of hydrocarbons in'which ali
with a resinifying agent.
10. In the treatment of partial oxidation prod-V
nets in the range from alcohols to organic acids
and containing hydrocarbon derivatives other
~ than acids, the steps consisting of separating from
phatic hydrocarbons predominate having’ a boil
ing point above 300°‘ C.
16. As a new composition of matter, the reac- '
the same a pluralty of fractions, each containing
25 a material percentage of derivatives other than 'tion product of sulphuric acid and a fraction boil—
acids, and sulphonating a‘heavier fraction whose’ ing over 300° C: of a mixture of oxygen derivatives
major portion- consists of bodies boiling over ‘of hydrocarbons in which aliphatic hydrocarbons
predominate, said derivatives being other than
300°v C.
a 11. In the treatment of a mixture‘ of oxygen acids and in the range from alcohols up to acids,
30 derivatives of hydrocarbons in- which aliphatic
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