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Патент USA US2133894

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Oct. 18-, 1938.
'T._S.HQDGINS
I
‘2,133,894
PROCESS FOR IMPROVING DRYING PROPERTIES OF OILS
Filed Feb. 26, 1937
8 Sheets-Sheet l
f
-5
.4
%ALKAL|NE
.5
.2
l
NEUTRAL
~0
.I
.2
%ACID
.5
.4
.5
o
'
'30
60
TIME OF GE.LAT\0N
<30
(HOURS)
I20
v
DNDEX
OF
REFRACTIOH
TIME
grvu cm/toc
ZdWOW
9%
Wjme) :
Oct. 18, 1938.
7
T. s. HODGINS
2,133,894
PROCESS FOR IMPROVING DRYING PROPERTIES OF OILS
Filed Feb. 26, 1&3?’
8 Sheets-Sheet 2
CURVES: MAXIMUM ALKAu-KMnm AND ACID KM"
0.50
%ALKAL!
0.20
O- I O
0.075
O. 050
I NEUTRAL
0.025
0.050
OJO
0.20
0.50
O40
053mm
aajyuym
Oct. 18, 1938.
T_ s, HQDGINS
'
2,133,894
PROCESS FOR IMPROVING DRYING PROPERTIES OF OILS
vFil’ed Feb. 26, 1957
4.
8 Sheets-‘Sheet 5_
'
I
'
OXIDATION CURVES OF UNTREA
SOYA BEAN OIL‘
SAMPLE
DESCRIPTION
‘
RAW soYA OIL-P‘PRESSMG
--
n
..
2'49
u
n
..
.,
5RD
.
--
--
.
IEXPELLORS, FILTERS
ALKALI REFINED SOYA on.
ARCHER DANIEL SPECIAL
RAW SOYA on. (SGAL. SAMPLE
Gum/mm
Oct. 18, 1938.
2,133,894
T. s. HODGINS
PN’ROVZNG DRYING PROPERTIES OF OILS
Filed.’ Feb. 26, 1957
8 Sheets-Sheet 4
(229. 5. '
ALKALl-PERMANGANATE SAMPLES
GELATiON
40V
0.025
0-050
0-075
0-400
25
3O
45
70
amen/for;
Oct. 18, 1938.
T, s, HODQNS
_
2,133,894“
PROCESS FOR IMPROVING'DRYING PROPERTIES OF OILS
Filed Feb. 26, 1937
8 Sheets-Sheet 5
Q09 6.
COMPARISON
6F
, KOH - KM" 04,
AND KMnO4 - HCI TREATMENTS 5.0.
TIME l5 THE TIME TO COMPLETE GELATION
%ACI 0
OR
7§ALKALI
2.0
HC' - KMnO4
TREATMENT
O. 8
0.2
O-l
HOURS
_
0
20
4Q
60
1343
>00
I20
0Z0
140
\60
160
v200
220
240
Gum/MA;
Oct. 18, 1938.
T_ $_ HODGlNs
2,133,894
PROCESS FOR IMPROVING DRYING PROPERTIES OF OILS
Filed Feb. 26, 1957
'8 Sheets-Sheet e
>
AClD - PERMANGANATE SAMPLES
SAMPLE
\%ACID
%KMNO4
O'O25
.
0.05
.
0.20
.
0-50
.
O- 75
I .00
GELATION l'N HOURS
50
60
‘
68
88
I00
.
H2
3%’ MW yyjwa,
Oct. 18, 1938.
2,133,894
T. s. HO'DGINS
PROCESS FOR IMPROVING DRYING PROPERTIES OF OILS
Filéd Feb. 26, 1937
8 Sheets-Sheet 7
HNO5 TREATED‘ SAMPLES
'
/
SAMPLE asunos eamyon?as)
Oct. 18, 1938.
T_ 5 HODGlNé
2,133,894
PROCESS FOR IMPROVING DRYING PROPERTIES OF OILS
Filed Feb. 26, 1937
8 Sheéts-Sheet s
9.
H1900
COMPARISON CURVES OF LINSEED
OlL. ?‘ TREATED, AND UNTREATED
0
IO
20
TED
SOYA OIL
INDUC
50
40
60
5o
4
ON
70
80
-
90
I00
no
120
flwmmhm
My £41m
Patented Oct; 18, 1938 ‘
UNITED STATES'
PATENT OFFICE ‘
2,133,894
_
v
raooass FOR maovnvc. DRYING
_ PROPERTIES OF OILS
\
Theodore S. Hodgins, Detroit, Mich., assignor to
Helmuth Beichhold, doing business as Reich
hold Chemicals, Detroit, Mich.
'
'
Application February 26, 19?], Serial No. 127,971
'3 Claims.
- This invention, relates to a process for im
proving the drying properties of raw oils by re
moving anti-oxidants therefrom, so as to render
the oils more suitable for use in the paint and
5 kindred industries.
-
(Cl. 260-423)
acid solution may be employed within the limited
alkaline or acid range to be more fully described ,,
hereinafter. This process effectively removes
the anti-oxidants (such as lecithin and 'kephalin)
, which are naturally occurring in these oils. 'ljhe 5
I am aware that previous attempts have been
made to improve‘ the drying properties oi oils
sludge containing the anti-oxidants and spent
by partially oxidizing the same, particularly by
in. any suitable manner, such as filtering or cen
passing air or other oxidizing gas through the.
10 body of theoil. My invention is not concerned
reagents may be separated from the re?ned oil
trifuging, depending on the nature of ‘the treat;
ing solution. In the case of alcoholic solutions 10
_ with this type of oxidation. .In such prior proc
the excess alcohol may be removed by distillation.
asses the oxidation ‘has taken place within the' '
I have determined by ‘numerous experiments
oil itself whereas according to my process only the optimum of acid or. alkaline values and this
the anti-oxidants are eliminated, the oil being will be ‘more apparent from a consideration vof I
15 unoxidized. Also in such previous treatments the'accompanying graphs, in which:
' ' usv
temperatures above room temperature have been ' Fig.’ 1 is ageneral graph showing the relation >
considered necessary whereas my process may be . between the acidity or alkalinity and the time of
carried on to best advantage at substantially
room temperature.
Fig. 2 is a general graph showing the conditions
gelation in hours.
7
-
_
.
.
-
20 ' ‘It has also been proposed to treat various oils - for'determining the length of time of treatment. 20
with chemical ‘reagents such asacids, alkalies
and salts for the purpose of improving their qual
ities, as for example for removing odors, or for
bleaching the same, but to my knowledge no
25 successful process has been carried out wherein
the anti-oxidants are removed by treatment at
room temperature with an oxidizing_ agent and
with controlled acidity or controlled alkalinity
‘ with respect to the oil.
30
'
_
According to ‘_my process I regulate the acidity
or alkalinity of'the treating solution, maintain
ing avalue only slightly on the acid or slightly
on the alkaline side. I ?nd that atithe neutral
point (pH of 7.0) it is impossible to ‘e?ectively
Fig. 3 is a speci?c graph showing the e?ect of
regulated quantities of- alkali and acid in the
presence of a constant amount of potassium per
. manganate in an aqueous solution.
Fig. 4 is a graph showing the'rate of drying of 25
a representative group of untreated soya bean
oils.‘
‘
-
a
'
- _Fig. 5 is a graph showing the rate of drying of
‘ soya bean oils treated with alkali-permanganate
reagents.
.
30
>
' Fig. 6.is a graph showing the comparative
e?ectiveness of various‘percentages of acid or
'alkali on the total drying time of oils treated with
various reagents.
_
.
' 35 treat the oil for the purpose herein set forth, and
Fig. '7 is a graph showing the rate of dryingof 35
also if the acidity. or alkalinity exceeds a certain ‘ . oils treated with acid-permanganate reagents.
predetermined limit which varies only slightly
Fig. 8 is a graph showing the rate of dryingof '
according tothe type of oxidizing agent em
ployed, the process becomes less and less effective
40 until a point is reached where substantially no
improvement occurs. Accordingly my process
consists in treating the oils witha relatively‘
Oils treated withfnitric acid reagents.
Fig. 9 is a graph comparing untreated soya
bean oils, treated soya bean oils and raw linseed ' 40
oil with respect to the time required to come to
complete gelation.
_
y
' strong oxidizing agent in low concentration with
45
The graphs are largely self-explanatory. It
respect to the oil,-‘and within predetermined lim _ will be noted however that the rate of di?usion is
its on the acid or alkaline side.
_
'
_
in5
The length of time required for treating-these ‘ ‘greater in the alkali process than in the acid
treatment.‘ The. rate of diiiusion _in turn is con
,oils is determined by the ?rst measurable in
crase in refractive index, or by a‘ corresponding
decreaseiniodine number. The method of treat
50 ment of an oil comprises treating the oil prefer
- ably at roomtemperature either with an aqueous
trolled by the rate of oxidation. _ The compound
formed by the reaction'between alkali and the
anti-oxidant is less stable than that formed by
the acid and anti-oxidant.
‘
'
,.
solution of oxidizing agents such as perman'—~
From the maxima of the curves, upward in
ganates, chromates, nitric acidv and the like, or ‘the case of alkali and downward for acid, it will
with organic oxidizing agents such as peroxides be noted that increasing amounts 'of acid or '1’
‘winanalcoholicalkalinesolutionoranaqueous
alkaliexert'arepressive e?ectonthereaction'. 55
2
8,188,804
This mixture is agitated mechanically using a stir
Excessive amounts slow down the reaction to sub.
stantially zero.
rer ‘or by blowing ?ltered air or an inert gas
'
‘Since the anti-oxidant is an amino compound through the material, it being understood that the
(lecithin or kephalin) it forms salts with the air or gas employed functions solely as an agitat
acids. These salts of the acid and amino com ’ ing means and does not in any way enter into
the reaction; This mixture is agitated from 1 to
pounds are more stable than the amino com
pounds and therefore harder to break down or 2 hours preferably at substantially room tem
decompose. With this thought in mind it is perature and thedecomposed impurities ?ltered
evident that the alkali will be more effective than
The exact time of treatment depends on how
10 the acid treatment.- Experiments have shown‘
this to be the case, the maximum acid concentra- - soon the anti-oxidant is destroyed.~ The com
tion based on the percent of acid per 100 parts plete destruction of anti-oxidants is determined
of oil being about two times the maximum alkali when the refractive index (Fig. 2) ?rst begins
concentration, 1. e., about two times more acid to increase. (The correlation between the index
15 than alkali is required to obtain the maximum on of refractionand iodine number was ?rst estab
the acid side than is required on the alkaline side. lished by A. M. Wagnet and J. C. Brier (Ind.
This relation applies only to the case of a process Eng. Chem., p. 40, Jan. 1931).) The resultant
out.
~
harder than the best re?ned linseed oil subjected
organic oxidizing agent may‘be summarized as
mhws-
to the same bake.
Alkali treatment
Example 2
Per cent
25
Alkali-(K011) _____________________ __
0.025
KMnO;
1.0
-
Hydrochloric acid _________________ .._
as described in Example 1, this process yields an
oil slightly lighter in color than the original and
possessing the same improved drying properties
Per cent .
0.05
36 KMnOr
1.0
referred to in Example 1.
Parts by weight
Time of treatment.-=%-8 hours.
Product.—-An oil slightly lighter than the orig
inal in color, which'goes to complete gelation in
>
35.
Example 3
Water (not constant) _______ __-_ _____ __ 1.0-10
_
.05 .
Using the above agitation time and tempei'ajture 30
Acid treatment
H01
1
'
Water (not constant) _____________ .._ v1.0-10
in 25 hours.
60 hours.
100
Potassium permanganate ____ __'_.._.._-
Time of treatment-5&4 hours.
Product._-An oil slightly lighter than the origi
30 nal in color, and which goes to complete gelation
40
Parts by weight 25
Perilla oil ________ _.. ________ .._~ ____ __
Water (not constant). ____________ __ 1.0-10
.
_
oil when baked one hour at 200° F. proves to be 20
The optimum treating conditions using an in
20
‘
oil is much improved in drying‘properties and
has a slightly lighter color. A ?lm of this treated
employing inorganic oxidizing agents in aqueous
solution.
‘
Oiticica nil
7
Sodium dichromate___;. _____________ __
100
1.5
Frm
_
0.3
While the optimum point for alkali treatment
is 0.025% it will ‘be noted satisfactory results may
Water (not constant) ______________ .._'.. 1.0-10
be obtained within the range of .013 to .40. The
preferred range however is from .013 to .050 as
Examples 1 and '2 and the ?nal product possesses
The operating conditions may be
described'in
similar characteristics.
45 indicated by the upper graph forming. part of
Examplev 4
Fig. 3. Likewise in connection with the acid
treatment while optimum results are obtained
with 05% acid, valuable results may be obtained
'
Parts by weight‘
Raw linseed oil ________________ -__..__.._
Sodium dichromate _________________ _..
1 between the range of .02 to .50. The preierred
range for the acid treatment is‘ from .025 to .050
_ as indicated by the lower graph forming partof
100 "
1.5
Sodium
Water (not
hydroxide
constant)
___________________
____ _-_ _________ _._
__ 1.0-10
0.3
50
Same agitation is in the preceding examples which
.
While in most of the above graphs soya bean' results in an oil ‘with improved drying" properties
oil was treated, comparable ‘results. are obtained as described in Examples 1 and 2. _'
.
I
While particular oils have been referred to in 55
55“ using other drying or semi-drying oils such as
linseed oil, sun ?ower oil, perilla oil, rape seed the preceding examples it will be understood that
oil and oiticica oil,'the variation in the graphs various other-oils may be substituted with simi
,using these other oils being of an‘ order of plus larly improved drying properties in the final
Fig. 3.
orv minus 5% of the values indicated in the graph. '
\ In the above graphs, the aqueous solution of
an .inorganic oxidizing agent was employed.
product.
I claim:—
‘
-
.
' 1. A process for improving the drying quality
of raw\oils containing naturally occurring anti
While the optimum point for oxidizing agents
oxidants, which comprises removing the anti
, is expressed as 1.0%, comparable results can be
obtained using the range from 0.5 to 1.5 parts oxidants from such oils by treating. the oils, at
'65 of oxidizing agent by-weight per 100 parts of oil. substantially room temperature with a relatively 65
The invention will be furtherapparent from strong inorganic oxidizing agent in concentra
the following speci?c examples which are in .--tion of 5-1.5 parts of oxidizing agent per‘ 100
tended as illustrative only and not as in any parts by weight of the oil, and maintaining the
way limiting the invention:
70
‘Example 1
I
pH value close to the neutral point while avoid-i
V’ V_
Partsby weight
Soya bean oil _____________________ __
Potassium permanganate, _________ __
Potassium hydroxide__-_' __________ __
‘100'
.
{
“
ing exact neutrality, by treating the oil with a .10
member of the group consisting of alkaline and
acidic reagents, the proportions employed in the
case of the alkaline reagent falling within the]
1
.025
75 Water‘ (not constant)“. __________ -.._... 1.0-10
range. of > .013-.050 part by weight of alkali. to
'
loopai'ts‘byweightottheoihandin?iecale 1|
3
3,183,894
3. A-process for improving the drying quality
of the acid falling within the range ‘of .025-.050
part by weight or acid to 100 parts by weight 01' of raw oils containing naturally occurring anti
the oil.
‘
oxidants, which comprises' removing the anti
2. A process for improving the drying quality oxidants from such oils by treating the oils at
of raw oils containing naturally occurring anti
substantially room temperature with a relatively 5
oxidants, which comprises removing the anti
strong inorganic oxidizing agent in concentra
oxidants from .such oils by treating the oils at
tion 01 .5-1.5 parts of oxidizing agent per 100
parts by weight of the oil, and maintaining the
pH value close to the neutral point while avoid
ing exact neutrality by treating the oil with an 10
acid, the _proportion of the acid employed fall
substantially room temperature with a relatively
strong inorganic oxidizing agent in concentra
10 tion of 5-15 parts of oxidizing agent per 100
parts by weight of the oil, and maintaining the
pH value close to the neutral point while avoid
ing exact neutrality by treating the oil with an
alkaline reagent, the proportion of the alkaline
reagent employed falling within the range of
.013-.050 part by weight of alkali to 100 parts
by weight of the oil being treated.
ing within the range of .020-.050'part by weight '
of acid to 100 parts by weight of the 011 being
treated.
‘
THEODORE S. HODGINS.
15
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