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Патент USA US2025804

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Patented’ Dec. 31, 1935
4
UNITED
* 2,025,804};
2,025,804
~
PROCESS FOR BREAKING PETROLEUM‘
v
a
;
EMULSIONSW
~
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-
‘ 'Melvin .De Groote, St. Louis, Bernhard Keis‘er, .;
'
, Webster Groves, and Arthur F. Wlrtel, Rich
‘ niond Heights, Mo., assi'gnors, to Tretolite Com-i
' panmuzlvebster Groves, Mo., a corporation “of 1
vlie Drawing.
Application December
v
>I
12' Claims,‘
Serial No.(Cristi-+74)
160,032
their
This invention, relates to, the , treatment ‘of
or, ems, by pressure oxidation at _'
relatively low temperatures,one mayemploy any
troleum emulsions, for the purpose of separating suitable unsaturated,,hydroxylated fatty mate-~
emulsions of mineral oil and water, such as pe
:the oil from thewater. I,
'
'
'-
a
>
.
' rial, such as castor oil, vricin'oleic acid. Idiricinoleic a
acid, material-of the kind described in the afore 5
‘I
Petroleum emulsions are of the ,water-in-oil
ca
type, and comprise ?ne droplets of naturally
mentioned application for patent ‘of DeJGroote‘
and Keiser, or any‘ other suitable material; ‘In
occurring waters or brines, dispersed‘ in a more
ourco-pendin'g application for patent Serial No.
constitutes the continuous phase of the emulsion. ‘750,031, ?led December 31,‘ .1934,I-we'ha've de-_' '
10 They are obtained from producing wells and from ‘scribed‘thepoly keto fatty a'cidsand their salts ,10
the bottom of oil storage tanks, and‘ are com and. esters Iasnewl'ccmpositions of matter, and I "
or less permanent state throughout the oil which
monly referredto as _‘‘cut oil", “roily'oil”, “emul
1 sided oil" and “bottom settlings”.
?
v
15
also a, new method for producing the ‘same,_i'.,e., '
pressure ‘oxidation at relatively» low, tempera- ‘ ‘
The object .of our invention is to provide a
tures,_such as 135° C. or less.
novel and inexpensive process for separating
.
_ .
.
I
v
I I
I
a
.
It is su?icient for the present purpose to ‘state ‘15 "
‘that the process ofour'said‘application for pat
ent produces materials hishin poly vketo fatty
emulsions of the character referred to' into their
component-parts of oil and water or brine. ,
I Brie?y described, our process consists in sub
acids,keto
which
fattyacids
have, thefsame
derived‘ characteristics,
by esterifying or,
as‘ ‘
jecting a petroleum emulsion of the water-in-oil f- poly
20 type to the action of a treating agent or_ demul
‘condensing a keto :fatty acid, such .as keto hy- 2o
sifying agent of the kind hereinafter described, I ' droxy fatty‘acid-wi'th ricinoleic acid or diricinoleic I
thereby causing the emulsion to break down and acid or 'oleicacid‘or triricinoiein;
I I
t I
I
separateinto its component parts of oil and water
orbrine, when theemulsion is permitted to re
Brie?y described, the method of producing ' I
such poly ketofatty acids by pressure oxidation, 1
25 main in "a quiescent state after treatment, or‘ is has disclosed inv our. aforementioned cc-p'ending
,
subjected ‘to other equivalent separatory pro
cedures.
'
s
,
i
I
_,
25
application for, patent consists in mixing an un
saturated, hydroxylated, fatty body of the” kind ‘
previously described, such as castor oil, with not I 2
'
Thetreating agent used’in our-process consists
of aI.poly keto fatty acid body or'r-bodies. "Itjis
v30 well known that certain fatty acids,_'=or_ fatty
bodies can ,be subjected tov treatment '50 85.110
over 110%.01 a true drying oil, such as linseed oil, ' "
or perillaoil, or the acids thereof, and subjecting '30 j
the same to pressureoxidation at approximately
~
yield keto I-fattylacids'kthat is, fatty, acids in r7115‘ tof'l5 lbs. ,I pressure by means of ordinary moist I‘ 7'
which 'a 'ketonic group {a carbonyl group) 'is
and'atv a temperature of-not over 135° (3., and .
present. One example is theconversion of ricin IIpreferabIy vat ‘about, 120‘? C., ‘for approximately
35
oleic
acid
into
ketohydroxystearicIacid.
‘Such,
__
I,
II
I
I
10I to.IIao'ihours‘, 'Asmau
amount
of aiia't'spnt.lasfi 4
ketohydroxystearic acid can be reacted "with ' ting'sulfonic \acid,I: such as ‘approximately I1/2%
other acids, particularly other hydroxy acids, to of Petrofrireagent (oil-soluble petroleumusulfqmc I
give polymerized acids, or more correctly, poly acids) maybe Present during oxidation,
I
Iketo acids which hayeythe same analogy to keto
a,
Ins well ‘known’ oil-course, that castor oilis 4o
I
"
acids as triricinoleic acid or diricinoleic ‘acid has‘ , an alcoho1,,.and in'fact, a secondary; alcohol. In
to ricinoleic acid.
I
I
~ ‘
‘is furthermore wen known'that litipme acids are -
.45
50
_ Poly keto fatty acids can be obtained byqthe produced by the -, cautious . ‘oxidation of marox'y.
cautious oxidation of unsaturated, hydroxylated, acids containing the, secondary alcoholic, “group,
fatty bodies of various kinds. In the-coe‘pending as, for example, oxidation'of‘ lactic 'acid'lto v‘pyrol- >
application for, patent of ‘De Groote and ‘Keiser, jraceinic acid; Insaid reaction the CH(OH)" group ;
Serial No. 760,025, died December 31, 1934, there is converted intoa CO] group. The cautiousoxi- -'
is described the=prcdiiction of unsaturated, hy-_ under
of castor
previously
oil ‘orspecified
ricinoleicacid
conditions
conducted‘
vresults I a a‘
droxylated, i’att -mate'i‘ial's_ obtainedby the oxi Idation the
dation ofrelatiye y- highly unsaturated, Inon in theyformation of aketonic Iacid,_-which may;
I
hydroxylatedjinaterial, suchlas semi-drying oils, ._be indicated by'thefollowingformulalw I :
'
‘.50
,
'
drying oils, marine oils, or their fattyacids or
; mixtures thereof,- The raw material, prior to‘
oxidation, is characterized by a relatively high
_'iodine number, such asl20~to 180 or'l90.
‘
a, - In the production of poly ketofatty'acids, or
v, v‘
>
I
a»,
__
‘ [cadence-poor!
.I
n ‘I
s
,
,However, oxidationnot only takes place at the
‘Ihydroxyl position, but
,
at the- ethylene link-‘.355 :
x
it‘
-
2V
"
.
'
acme-o4
age, with probably the absorption of oxygen and
cluding the meaning of "aldehydic” in the sense
then conversion into hydroxyl groups, and thus
previously described or discussed, 1. e.,- that both
urated, dihydroxy, acid which may be indicated
their ultimate composition in carbon atoms, hy
drogen atoms, ‘and oxygen atoms is identical.
the ketonic acid produced‘may represent a sat- ' have the carbonyl ‘(C0) radical present, and
by the following formula:
“
p
> v
5
‘ It‘is understood, of course, that these polymer
. ized ketonic acids or their esters maybe con
' verted into salts, or esters in the manner, gener
However, it is well known thatmxidaticin re
10 actions tend to'polymerize orform ester ‘acids,
ally- employed ‘for the manufacture of salts or
‘However, it should be borne in mind that 10‘
saponi?cation of, the kind which would decom
.o. esters.
ethers, etc., and thus the resultant product rep
resents ketonic acids in the polymerized form, pose the'polymerized material into its simpler
1. e., derived from two or more molecules, at leastv form‘ in the same, manner that diricinolein could
, bedecoinposed into two} molecules of ricinoleic
one of which must contain a’ ketone group; '.
v"ll'he formation of ketohydroxystearic acid in acid, is objectionable‘ and cannot be employed. 15
the usual manner (see Lewkowitsch, “Chemical Due to the low cost of castor oil and the low
Technology ‘of Oils,.Fats and Waxes", 6th edition,‘ "cost of the hydroxylated unsaturated materials
volume 1, page 240) with subsequent reaction‘ described in the co-pending‘De Groote and Keiser
with ricinoleic acid, diricinoleic acid, ,oleicacid, application for patent previously referred to, it
so happens that the products commercially pro- 20
20 triricinolein, etc., results in a compound repre
‘senting substantially nothing'other than "poly ‘ duced'will be‘d'erived from esters as raw mate
keto acids. On the other hand, we are aware that
the’ productsobtained by pressure oxidation in
the manner referred'to previously,_inay result in
products containing a ‘significant amount or
25
majority of poly keto acids, but “may "contain
rials‘and that the amount of free acidic mate
rial, after pressurejoxidation, is relatively low.
In such instances where-it is desirableto elimii
nate this residual acidity, ‘it is best accomplished 25
by means of a relatively weak base,“ such as tri
certain" other non-vketonic material of vthe kind ' ethanclamineas in the case of thepreferred ex
presenti in‘various conventional or special‘ blown " ample,1which will be described ‘subsequently. In
7
oils. ‘Since such non-ketonic materials are also I some‘in'stancea'it might-be desirable'to mix an
effective quite frequently for ‘the treatment of
30
oil field ‘emulsions, we prefer tov use the impure
form-of‘ poly keto acids or their salts or esters,
as obtained by pressure oxidation. This ,is a
alcohol, particularly ‘a polyhydric alcohol, such 30
as glycerine or ethylene glycol; with the pressure
oxidized bodies and'the'n heat'so as to, eliminate
the carboxylic hydrogen. In any event, the ‘poly
meria'ed' ketonic bodies 'may be converted; into
matter of pure economy. The pure forms, rela
35 tively free, from extraneous materials, ‘maybe ' any suitable form by means‘of conventional re- '35
actions,'provided that the material is not ‘de
' employed.
‘we are fully aware that migraajosimsy take
7 place in a fatty molecule‘. For instance, that the
formation of stearolactone from, hydroxystearic
composed so as to destroy the carbonyl radical
‘or the polymerized state, and thus produce'simple
ketonic fatty acids, 'as differentiated from poly
acid appears to depend on the migrationof‘ ‘ the "ketonic acid acids in the same’rn'ann'er as ricin- 40
alcoholiform hydroxyl. We are also, aware that oléic acid-isdifferentiated from diricinoleic acid.
The manufacture of the demulsifying agent
in, the case of‘the common'non-fattygketonic
process, ,
acid, aceto-acetic‘acid, that certain-reactions are that we ‘prefer to use in practising‘our Approx
known to‘ take place ‘which suggest that aceto ‘ is carried‘ out in the following’ manner‘:
acetic‘ ‘acid may,‘ as far as those reactions are imately-‘4,000 lbs.'of castor oil‘are placed'oiyn a 45
concerned, react more‘ as an aldehyde or" as ‘an ‘ vessel of‘ a‘ convenient kind equipped‘with a suit
aldehydic acid than‘as a ketonic'acid. [Such able means for heating the same to approximately
"wandering of- a hydrogen atom. and changefin ' 135°‘C.1and also for coolingthe heated‘mass, if
positiqnof a double bond is referred to as ket'oé ' desired. Similarly, the vessel should‘be equipped
50 enolic ‘tauto'rnerism (Bernthsen, 1 “Text ‘ Book of ‘ ‘for? maintaining - pressure ‘during oxidation at 50
Organic Chemistry”. ' 2nd edition, 1931, pagev ‘(any desiredpoint, such as 45 lbs.‘ or as‘much as
231).; We believe" that this or‘ a comparable ' '75 lbs. ‘ To this castor oil there‘ is ‘added approx
change may talsej place in these poly ketonic acids " imately 400 lbs.‘ of linseed oil‘o'f either the boiled
or bodies previously described, and possibly in type, with added-metallic driers, such, as cobalt,
‘ 55
regard to some reactions,'these vpoly ketoacids linoleate, manganese, 'resinate, etc.,: or'the un- 55
or esters thereof act more as if they were alde
‘ boiled-type. - Approximately 40 lbsQor lessof Pete‘
be incompatible,‘ it isvalso likely'that 'thesepoly
ketonic acids" or their‘ esters may be incompati
ble, for the reason that’th'ey really mayibe alde
, maintained during oxidation at approximately 60
‘presence of the carbonyl group, in ketones'also
with an‘ alcohol, partioularlyapolyhydriealcohol, 65
hydio acids or esters or saltsjthere'of. In other roif agent 'are'added. " The mass is then heated
words, if these'polyxketonicacid‘bodiesyare to -up to approximately 125° C. and ‘1 oxidation, by
started, and-the" teinperaturev
‘be used in a mixture where aldehydic acidsfwould ‘means of air,
o 60
120° C.‘ Oxidation is carriedpn- for ‘approxi- -
mately 20 hours.‘ At the end of ,the oxidation
hydic acid bodies.’ It is to ‘be noted that the re‘ period the material will show some=free carboxylic .
‘ agents of thekind-employed for determining the . acidity, which may be'removed by esteri?cation
65
usually detect the "presence of, the carbonyl such as‘glycerine‘ or ethylene; glyco'Libut we 'pre- group in aldehyde's. ‘It is tobe understood that afer to eliminate the acidity',,if“desired, by the
addition‘ of an" equivalent amount: of ' triethanol
" in theclaims where "the products are character
ized' by the presence of ketonic radicals,- that such amine: The product‘so obtainedis ready forluse
; :7-0 , acids
might ultimately prove to be‘ aldehydic' " in breaking on field emulsions‘, ‘feith'er ‘alone?onin 7o
acids, or at least convertible under certain con.
ditions of use, or else under certain conditions of
, 75
suitable admixture with other‘ reagents or'd'e‘mul
sifying agents.
In many instances the‘ most eta‘ , ,
' identi?cation, possibly they become converted into j'ffectivetreatment is obtained without the?nal '
" aldehydic' acids, and it is'"not intended 'that'fthe neutralization with iriethanolamine.‘ , As a mat
word f‘ketonic" orv "keto” be-interpreted as ex-‘-'
7'ter of practical convenience, 1'we 'prefcnto'dilute
~'s‘,os5;e’o4
.I
I
_
Ithereage'nt with'50 % by weightof'a- solvent ‘com ‘upon the, emulsion tobfe treated,j1n1'anyiortne. _ I
posed of 'equal'volumes of‘ solvent naphtha and
,various‘ways or by any ofthe venous apparatus _
methyl alcohol.
now generally used to resolve ‘oribreakpetroleum .
,
‘
-
‘- The use of demulsifying*agents-consistingI-of' iemulsions with aI'chemIcIaIIIreagent. ' '_ I,
, M >
various sulfo-acids,~"or 'carboxy"‘acids, or ‘com ,f {Having'Ithus described our-"invention, what e“? 5 ,
pounds having both a sulfo group and a carboxyl
claim as new anddesire to‘ secureby Letters , at- ,
group; 'is'well- known in the treatmentof water-. I '
in-oil‘emulsions;
entisij
]
a
,
.
..
,.
V
{1.‘IiAY
a petroleumemul-v
__ I process'IIfor'breaking
I
I
I
I
I
_
,_
In the use of conventional de-'
I,
mulsifying ‘agents it is the-common practice to ‘ sion‘ofthe‘watereineo? type,‘ which» consistsdn‘f
10 use them not only in the form of acids, but also subjecting the emulsion to theaction of, a de-i
.
10
I
in the form of salts or esters, or half salts, or
half esters, or ester salts, in case of dibasic acids.
mulsifying agent comprising a ‘poly keto fatty
The salts generally employed are the sodium salt,
, 2. ‘A process for breaking a petroleum emul-i " '
potassium salt, ammonium salt, calcium, magne
sion of the water-in-oil type, which consists in‘
acid
body.
»
‘
-
‘
'
‘
'
15 sium, the triethanolamine salt, etc. The esters : subjecting the emulsion'to the action of _a demul- 15‘ _ , _ ‘
' may be employed such as the methyl ester, ethyl sifying agent comprising a poly'keto fatty acid a
I * ‘
ester, propyl ester, butyl ester, amyl ester, hexyl
ester, cetyl ester, etc. Aromatic or cyclic ester
bodyinthei'ormoi’asalt,
may be employed. What has been said in regard
20 to the use of conventional demulsifying agents
applies also to'the materials employed as the
demulsifying agent of our process.
‘
y i .
~ ‘
derived
4. Aprocess
at leastforinbreaking
part‘from
a petroleum
castoroil.’emulsion
'
, ‘ofv the water-in-oil type, which consists in sub-
4 , I
‘ ,jeeting the emulsion to the action .of a dem'ulsi- 25 ‘
such‘ as benzene,'~toluene, xylene, tar acid oil,
Alcohols particularly -'
. § ‘
tying agent comprising a poly ,keto vfatty acid '
gasoline, kerosene, stove oil, a coal tar product, ‘
i _ cresol, anthraceneoil, etc.
,1
fying agent comprising a poly keto fatty acid body
Conventional demulsifying agents employed in
such, or after dilution with any suitable solvent,
such'as water, petroleum hydrocarbons, such as
,_
voi! the water-in-oil type, which consists in sub,
jeoting the'emulsion to the action’of a demulsi- 20- -
the treatment of oil ?eld emulsions are used, as
1,25
,-
3. A process for breaking a petroleum emulsion
body in the form. of a salt,~derived'at least in part‘
-
from castor oil._'
-
>
Y
,
,
; v. 7
5. A'process for breaking a petroleum emul-é. ,
>
. ,
30 aliphatic alcohols,‘ such as methyl alcohol, ethyl I sion of the water-in-oil type, which consists in 30; - ‘
alcohol, denatured alcohol, propyl alcohol, butyl subjectingthe emulsion to the action of a de
alcohol, hexyl alcohol, octyl alcohol, etc. may be Imulsifying agent comprising a poly keto fatty
employed as diluents. Miscellaneous solvents, ' ‘acid body derived by pressure oiddatlon of caster
such as pine oil, carbon tetrachloride, sulfur diox , oil at a relativelylow temperature. a ' - I ‘I " '
35 ide extract obtained in the re?ning of petroleum, f . 6. A process‘ for breaking a petroleum emulsion 35 “I
etc. may be employed as diluents.‘ Similarly, the of the-.water-in-oil‘ type, which consists in sub-'
: ~
material or materials employed as the demulsi
.iectingagent
the emulsion
comprising
to the
a poly
action
keto
of ‘fatty
a demulsiacid ~ fying agent of our process may be admixed with‘ . l-i'ying
one or more of the solvents customarily used in body in the form of a salt, derivedby pressure
I
40 connection with conventional demulsifying agents. ' oxidation of castor oil at a relatively low temf 40v I
Moreover, said material or materials may be used
alone .or in admixture with other suitable well
7' known classes of demulsifying agents, such as
perature.
,
'
'l. A process for breaking a petroleum emulsion >
of the 'waterkin-oil type, which consists in sub- '
demulsifying agents of the modified fatty acid
.iecting ‘the ‘emulsion-to the action of a demulsi- I .
45 type, the petroleum sulfonate type, thealkylated
fying agent obtained by the pressure oxidation 45
sulfa-aromatic type, etc.
,
.
It is well known that conventionaldemulsifying'
at relatively low temperature of castor oil- ad- .
mixed with a small amount of a true dryingoil. ‘ _
agents may be used in a water-soluble form, or
8. A process for breaking a petroleum emulsion I
in an oil-soluble form, or-in a’v form exhibiting ' of the water-in-oil type, which consists in sub»v
50
both 011 and water-solubility.‘ Sometimes they
may be used in a form which exhibits relatively
‘ limited water-solubility and relatively limited oil'
jecting the emulsion to the action of a. demulsi- 50.‘
fylng agent obtained by the pressure oxidation.
at. relatively low temperature of castor oil ad
However, since such reagents are 1 mixed witha small amount of linseed oil.
9. A process for breaking a petroleum emulsion
sometimes used in- a ratio of l to110,000, or 1 to
55 20,000, or lvto 30,000, such an apparent insol - of the water-ineoil type, which consists insub-Y
, solubility.
ubility in oil and water'is‘not signi?cant, because jectingthe emulsion to the actioneof a demulsia
said reagentsundoubtedly have solubility within iying agent obtained by the pressure oxidation '
the concentration. employed. -- This same fact is at relatively low temperature of castor oil ad-~
true in‘regard to the material or materials em " mixedwith not ‘over 10% of linseed oil;v
60 ployed asIthe demulsii’ying agent of our process.
As stated previously, it has been so common to
; 10. A process for breakinga petroleum emul
sion of the water-in-oil type, which consists in
use, aiconventional ,demulsifying agent derived subjecting the emulsion to the action ofja de-I
froman'acidin the-form oithe acid itself, or in mulsifying agent obtained by, pressure oxidation
the form of a'salt',for.in}the form-ofan ester, that ' at approximately 45 lbs. pressure ofcastor oilad
the expression‘ “acid body” is ‘frequently-employed ' mixed'with not over 10% oflin‘secd oil and said ‘
to mean the acid ‘itself, or
‘ester? thereof,-:-or ,
‘ salt thereof. The word “body’fIis'j-hereiniemg
ployed in this'same sense in conformitywithiits; ’
‘oxidation being conducted ata- temperature-.0!
{approximately-120°C.
11‘; A: process-:ior
_
I I
'
a petroleum emu]? g
' prior usage in the trade, and particularlyin vari ' sion at the waterside-oil type, which consists in
bus patents of the prior art. Half salts and half subjecting'the emulsion to the-action of a demul- 70
esters are considered as salts,’ and esters, respec_—_ Isifying agent obtainedby pressure oxidation at
tively.
I
approximately 45 lbs. pressure of‘lcastor oil adq- ,
In practising ourprocess a treating agent or mixedliwith not, over 10% of linseed oil and said
,demulsifying agent of the kind above described ‘oxidation being conducted at a temperature of
75 is brought into contactIwith or caused to act
approximately‘ 120° .C.,rfollowed by neutraliza-r 78'
‘ r ’
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1.99m“
rtion of the earbonlic hydrogen present by means ' ,v ‘approximately! 1209
‘uttrlethnnolamin'ef
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0., fqllowed by‘neutra?zeti‘on ‘ ‘
' ,0! the darboxylicy hydrogen presen?bymeans p1’ >
I 12‘./A‘p1‘_oces>s 1017 breaking ‘a’ betroleurnjemnlé triethanblainine, said mass then being admixed‘
slon 01' ‘the waten-in-o? type,vwhieh consists‘nin v{with 5V07qvwye1ghtpt a, solvent; consisting'ot equal >
' subjectingthe emulsion tq‘ thenctibrl of a. demul ‘ PM“. 0! methyl $190110! and solvent naphtha! ; j a a
drying agent Qbt'ained by pressure " oxidation ‘at ‘
mixed
approximately
with not'45’
over
lbs.10%
preésu'rebf
0t linseedoil
‘cnsto'ran'dlsa‘id
o?wad- ' ‘K
_
“oxidation being conducted fat 2. tempernture ‘of
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BERNHARD
m'rnugmwm'mn.
KEISER. ‘ ‘
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