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Патент USA US2411105

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Patented Nov. 12, 1946
Alan C. Nixon, Oakland, and David Louis
Yabro'fl", vBerkeley, Calif., assignors ‘to 'Shell' 'j
Development Company, San' Francisco; Calif‘;
a corporation of Delaware
No Drawing; Serial
.No. 506,612.
\ .
10 Claims. ~(Cl. 196—"-30)?=
solution is then re-used for treatment of further“
This invention deals with a method for improv
quantities‘of the original mixture;
ingvthe rate of separation of alkaline treating
The mixtures. to which-this invention is appli- ‘’
liquids or solutions from hydrocarbons or of facil
itating‘steam strippingof the resulting fat alka-~
cable‘are either normally liquid or normally gas- ‘ '
line solution, if the latter is desired,- or both. This
eous andip'referably have "an end ‘boiling point
of below about 200 C. They are comprised of *
inventiontis a continuation-in-part of our. co
pendingapplication SerialNo. 394,004 filed May -
sulfate ‘ester acids,
and‘ must
be substantially
3431618301‘ otherv
It .is.we1l known that hydrocarbon ‘oils are I tively strong acids because of the effect‘ of thesev "
10 acids upon the alkaline‘ treating solutionlby per- ‘
manently poisoning or neutralizing it. '
pounds of ma-nyxdi?erent degrees of saturation, '
mixtures of hydrocarbons and may vcontain com
Alkaline‘ treating liquids‘ or solution which may
such‘as paraf?n's, ole?ns, polyole?ns, acetylenes, i
naphthenes; or aromatics. It is also knownthat ~
hydrocarbon :oils frequently. contain-weak acids -
be employed‘ must be stable and'inert so as not ' >
10-5, such as hydrogen sul?da'mercaptans, alkyl
theyvmustihave a greatersolvent power for some" "
to react irreversibly with the components of e. g. havingrdissociation constants below about‘ 15 thei‘mixture‘under'the conditions of the process?”
componentsthan for‘ others; ‘and they ‘must be -
phenols; etc. :It is often desirable to treat such
separable‘from the dissolved components by phys
hydrocarbon mixtures :to separate‘the'm .intohy- .
ical means such;as,.;by ‘fractional distillation‘ '
‘drocarbons'vof different ,d'egreesof saturation'for ;.
washing out; either while they‘ are in the
to purify particular hydrocarbons, hen-12:20 and/or
form originally’absorbed or else after they’ have
zene-,:~.tolue‘ne, xylene, ‘butylenes, buta'dienasiso;
been changed chemically by a simple operation" -
prene,_ethylene; acetylene, etc.-; or to remove-weak .7 .
acids of theztype-mentionedv above .from such: .
hydrocarbons or mixtures. ' »
Onemethod of carrying outsuch-a separatiorn
such as air oxidation. " If employed in liquid ex- '
traction,:they must‘ be only partially miscible with‘ '
25 inixtur'es'to bejextracted». " They maybe aqueous
or non-aqueous;
or puri?cation is by extracting one~or more-oi
the components with an alkaline solution‘; which
Some ‘speci?c examples'of alkaline treating liq!- '
uids for the ‘separation of unsaturated hydrocar= '
hasv a» preferential lsolvent powerior one‘ or more- '
bons from mixtures containing them are: aniline,‘ ‘
of the components of thelmixture, and there; 30 methyl‘ aniline, toluidine, etc: solution of complex ‘ -'
after Isaparating the resulting alkaline ‘solution-‘'7 ~
from vthe dissolved portion of the mixture.
‘The '
extraction'maybe either-by liquid-liquid_or by" =
vapore‘liqui'd contact, including extractive-‘distil- ~
salts 'of univalent heavy metals from groups I and "
II of the periodic‘table, such as copper, silver, *'
gold,vmercury, etc;; 'chlorides',"nitrates, cyanidesi"
lation. "(In order'to achieve separation by eXtrac-"
acetates; etc., with ‘anhydrous; aqueous, alcoholic, ’ "
eta,‘ ammonia or'lower organic aliphatic-primary; ‘ '
tive distillation thev two“ or more compounds to be
saparated‘ from' one another should as a rule boil
amines, such as methyl amine, ethyl amine, propyl . '
not'more than ‘about‘20°' C. apart'an‘d preferably ‘
not‘more thanabout=10° C, apart.) These ex- J
amine, butyl amine, ‘ethylene diamina-nionon di-,
or tri-ethanolamine, or quaternary ammonium‘.
bases as tetra methyl, trimethyl benzyl, ‘etci; am"- ' "
tractions are normally carried out in apparatus 40 monium 'bases,.etc. In the extraction of weak
permitting contact of the alkaline treating solu--'
acids normally ' associated ‘with petroleum, oils,‘
tion ‘and the mixture containing the hydrocar
alkaline treating solutions; such as tripotassium ‘
phosphate, sodium phenolate, sodium borate,'so- ‘L
bons, usually.‘ by counter-current flow, .either
through a packed or a plate column, or through a
dium. or potassium carbonate, ‘organic bases, such
series-of mixers and settlers, whereby two end 45 as ethanolamine, ‘diamino propanol, piperidine',‘
etc:, or strong solutions of alkaline metal'hydrox- .,
phases are produced and separated, one of which
is an extract comprising the ‘fat alkaline treating
ides,‘ preferably'having concentrations of 25 to '
solution containing theextracted portion of the
50%“, or alkaline solutions containing solutizers '
may be employed.
mixture, and the‘other of which is the 'raf?nate
Solutizers are known‘ as organic substances
portion of themixturie. These two phases may be 50
which when in the ‘liquid state are solvents for
both liquid or one. may be liquid and the‘ other may
weak organic acids, are substantially insoluble in .
be aJVapor, For‘ reasons of economy, the fat'alka
Water-immiscible: liquids, are soluble in aqueous
linesolutioh .is' usually regenerated such as by
strong bases, are chemically inert to the action‘
steam, stripping, air blowing or washing with a
of said bases even at elevated temperatures," and
suitable‘ wash liquid, " etc, and the‘regen'erated
have boiling temperatures preferably substan
It has been discovered that the addition of rel
atively small amounts of a stable organic surface
active agent which contains at least 8 carbon
atoms per molecule and has a molecular weight
of below about 1000 (preferably below about 600)
and which is dispersable in the alkaline treating
iially higher than water. Solutizers are used to
enhance the extractive powers of aqueous alkaline
solutions for weak organic acids such as mercap
;ans and phenols. The solutizer process and the
various solutizers have been described in a series
3f patents and patent applications as well as in
;he general literature, for example, in the Yabroff
at al. U. S. Patents 2,149,379, 2,149,380, 2,152,166,
liquid, results not only in reducing'foaming and
in an improved rate of separation, but also in
effective and rapid breaking of emulsions which
2,152,720, 2,152,723, 2,164,851, 2,186,398, 2,202,039; 1O may form between the two phases produced in the
process. It is important that the agent be readily
applications Serials Numbers 255,684, ?led Feb
and completely dispersed through the treating so
."uary 10, 1939; 271,962, ?led May 5, 1939; Re?ner
lution so as to be continuously and evenly effec
and Natural Gasoline Manufacturer, May 1939,
tive throughout ‘the entire zone of contact and
pages 171-176, and March 1940, pages 73-76, In
the surface-active agents used in the process are:
:lustrial Engineering and Chemistry, volume 32,
those which form true solutions in the treating:
pages 257-262, February 1940, etc.
solution or spontaneously form colloidal disper
In choosing one of the above alkaline treating
sions therein, i. e. form dispersions of at least col
liquids, sight must not be lost of the boiling tem
loidal dimensions.
perature requirements relative to the boiling tem
The agents should be reasonably stable toward
perature of the mixtures. For example, in vapor 20
the action of oxygen in the presence of caustic.
liquid extraction, it is important that the solvent
chosen have a boiling temperature higher than
alkali and at elevated temperatures of steaming:
if steam regeneration is employed as part of the
that of the mixture to be treated, and in the spe
ci?c case of extractive distillation, it 'is desirable
In a regenerative process wherein the spent
that the boiling temperature of the solvent be not
less than about 50° C. higher than the boiling
treated solution is continuously regenerated and
temperature of the mixture. Accordingly, the
recirculated for further contact with the mixture
particular treating agent to be employed neces
to be treated, it is desirable that the surface-ac
sarily depends upon both the boiling temperature
tive agents, in order to be more or less perma-v
of the mixture to be treated,- and the: type of
nently useful, should not be extracted from the
process to be used in the treatment.
treating solution when ‘the latter is contacted
with the hydrocarbon mixture. ‘ The presence of
Unfortunately, processes of this type often pro
the agent in either of the separated components
duce foam and/ or emulsions which greatly reduce
the maximum throughput of a given treating
of the mixture may be undesirable, as it may in
terfere with their intended uses. Therefore, the
unit. Emulsions, if formed, occur in liquid-liquid
treating, and foaming may occur in vapor-liquid
surface-active agents should be substantially in
treating. Foaming may also occur if distillation,
steam stripping, air blowing etc. is employed as
soluble in hydrocarbon oils.
a means for recovering the alkaline treating so
lution from the extract or ra?'inate.
these agents from the treating solution in which
The nature of the substances responsible for
difficulties is not de?nitely established. It is be
lieved though, that foam and emulsions are pro
duced by small amounts of impurities, such as
possible such separation.
'In some cases, it may be desirable to remove
case they should have a property which makes
compounds related to gasoline gums or similar ~
The organic surf ace-active agents of this inven
tion are organic compounds containing at least
one atom of sulfur and/or oxygen. More’speci?-v
cally they are members of the following groups:
resinous materials formed by reaction of some of
sulfonic or sulfuric acids having at least one alkyl
the components of the hydrocarbon mixtures
radical of more than 4 carbon atoms, naphthenic
acids ‘having molecular weights between about 250/
and 500, fatty acids having between 8 and 14 car
bon atoms per molecule, and the corresponding
alkali and alkali-earth metal salts of each of the
above free acids. Such surface-active compounds
with themselves or with the alkaline treating so
lution or a component thereof, particularly in the
presence of oxygen. In many cases it is impos
sible to keep air away from such mixtures, since
small quantities easily leak vthrough joints of _
pumps and valves, etc.. Thus, most hydrocarbon
ails contain small but de?nite amounts of dis
may be generally represented by the formula RY,
solved oxygen. .In the case of treating solutizer .
solutions with alkaline solutions containing
ohenolates, a phenol type resin- may be formed,
for instance, by the interaction of mercaptans,
aldehydes or other impurities in the mixture
Accordingly, it is the purpose of this invention
;0 provide means for improving, the rate of sepa
cation of aqueous alkaline treating liquids from
;he hydrocarbons which are being treated. An
ither purpose is simultaneously or independently
;0 reduce the foaming tendency of the treating
wherein R is an organic radical and Y is a polar
radical containing an atom selected from the
group consisting of oxygen and sulfur. -
Some of these agents are known to be‘ more
effective for breaking or settling emulsions, others
are more effective for breaking or reducing foams,
while still others are effective for both.
. Agents which are generally effective to prevent
or break both foams and emulsions are the alkali
and alkali-earth metal salts or free acids of sul
fonic and sulfuric ester acids (containing an alkyl
radical of more than 4 carbon atoms) ,.of naph
thenic acids (having a molecular weight between
iquid, for example, when it is being regenerated
250 and 500), and of fatty acids. (having between
)y steam stripping. Still another purpose is to
8 and 14 carbon atoms per molecule).
provide means for preventing the formation of
The sulfonates and sulfates may, if desired,
zmulsions caused by the presence of emulsi?ers 70 contain non-functional radicals such as halogen,
n_ the treating liquids, particularly those con
vaming impuritieswhich readily react to form
emulsi?ers. It is yet another purpose to provide
t remedy for breaking emulsions formed in such
reating processes.
ether, amino, imino, hydrosul?de, sul?de, ester,
carboxyl amide, etc, radicals. Free carboxyl
radicals should preferably be absent in the sul
fates and sulfonates since some sulfated or sul
75 fonated fatty acid soaps cause violent foaming.
Speci?c sulfonates which we have found to be
suitable for our purpose are, for example, water
soluble alkali metal salts of petroleum sulfonic
acids such as the salts of “green acids” produced
in the manufacture of medicinal oils by acid
treatment; or of the products of treating kero
sene or lube oil extracts with strong sulfuric acid,
etc.; or of various aliphatic or alicyclic sulfonic
acids such as fatty sulfonic acids, fatty aromatic
sulfonic acids, naphthene sulfonic acids; or of
sulfonic acids of various alkylated (containing an
alkyl radical of more than 4 carbon atoms) ‘ten
zenes, diphenyls, xylenes,‘ diphenyl methanes,
naphthalenes, anthracenes, phenanthrenes, tet
thenic alcohols obtained in the catalytic reduc
tion of fatty or naphthenic acids, alcohols ob,
tained by condensation of ketones or aldehydes
followed by a hydrogenation; or alkyl aromatic
mono esters of sulfuric acid, etc. A convenient
source for many of the active sulfate ester acids
are the sludges obtained in the acid treatment
of cracked distillates, or the spent acids obtained
in the polymerization of ole?ns or in the alkyla
tion of isopara?ins with ole?ns with sulfuric acid.
The alkali or alkali-earth salts of naphthenic
acids having a 'molecular‘weight between 250 and
50,0,may, be derived’ from petroleum and‘ may
comprise a mixture of salts having molecule
ralines; phenols (derived from petroleum or coal 15 weights within this range.
tar distillates) ; chlornaphthalenes, diphenyl ox
The salts of the fatty acids containing between
ides, chlorinated diphenyl oxides, diphenyl sul
?des, diphenyl amines, phenyl naphthylamines,
dinaphthyl oxides, sul?des or amines, pyridines,
quinolines, isoquinolines, pyrroles, pyrrolidines,
piperidine, thiophenes, thiophanes, etc.; or of
various sulfonic acids of carboxylic acid esters or
amides, such as for example, of the ester sulfo
carboxylic acids or sulfonate amides having the
general formulae:
(0:41-01? )n , O=(|J—R’
8 and 14 carbon atoms per molecule such as sod
ium or potassium caprylate, pelargonate, caprate,
undecylate, sabinate, laurate, tridecylate, myris
tate, etc., are effective both as demulsi?ers and
However, the salts of lower fatty
acids, those having less than 8 carbon atoms and
those having more than 14 carbon atoms such
as stearic acid, are substantially ineffective. .
Amounts of the surface-active agents which
need to be added to improve the rate of settling
or breaking vof the emulsion or foam or both,
are insufficient to materially affect the action of
respectively, wherein the R radicals are organic
radicals of more than 4 carbon atoms such as all
phatic or cyclic hydrocarbon radicals, M is an
alkali metal and n is an integer normally not
the treating agent. This amount, may vary, be
tween about .001% and 1%, and preferably be
tween about .001% and .1% by volume of the
treating agent. The different types of treating
agents are capable of dissolving different amounts
of the surface-active agents and different mix
35 tures may require different amounts to reduce
While the carboxylic acid esters and amides
foaming and/or emulsi?cation. This is probably
listed above are very effective for our purpose,
due to the difference in reactivity of the ions of
many of them have the disadvantage of being
the respective agents and their effect on the hy
susceptible to hydrolysis during steam regenera
tion of the treating liquid forming free carboxy 40 drocarbon'mixtures treated. Therefore, actual
laboratory tests within the above limitations may
lic acids upon decomposition, the salts of which
be required to accurately determine the‘ amount
may cause foaming unless they have 8 to 14 ca of the agent or combination of agents for the
bon atoms.
most effective separation of the given mixture
It is of interest to note that the alkali metal
with a given alkaline treating solution.
salts of sulfonic acids possessing at least one
It is desirable that the bene?cial effect of the
alkyl radical of more than 4 carbon atoms, are
shall‘not be restricted to and be dependent
in general far more effective than the salts ‘of
on a speci?c range of concentration substan
corresponding sulfonic acids not possessing them.
tially narrower than the limits indicated aboVe—
For example, the alkali metal salts of naphtha
that is to say, there should not be a sudden re
greater than
lene or anthracene sulfonic acids such as mono-‘
or dibutyl phenyl phenol sodium mono- or di
sulfonates, sodium tetrahydro naphthalene sul
fonate, i-sopropyl naphthalene sulfonate, etc., are
only mildly bene?cial if at all in carrying out
the purpose of this invention, whereas the cor
responding salts of higher alkylated naphthalene
versal of the bene?cial effect, 1. e., an increase in
the emulsi?cation or foaming tendencies or both,
of the extracting solution upon addition of a
slight excess of the salt over the optimum quan
tity. On the contrary, the bene?cial effects
should extend over substantially the entire range
of concentration indicated, and changes in the
sulfonic acids are highly effective.
- effects due to-deviations from the optimum con
The sulfonates may be prepared in various
ceh'trati'on should be only matters of degree.
ways. Aliphatic sulfonates may be obtained
Many surface-active salts. particularly the ordi
under some conditions by treating ole?ns 'or di (ii) nary soaps such as sodium stearate, sodium
ole?ns with strong sulfuric acid; or by treating
oleate, etc., effect de-emulsi?cation in certain
organic acid sulfates with sodium sul?te so as
speci?c amounts. However, when present in
to eliminate sodium sulfate; or by oxidation of
slightly larger amounts increase, rather than de
mercaptans with nitric acid, etc.
crease, the emulsion tendencies of the extracting
Sulfate ester acids, the alkali salts of which (if) solution. For example, sodium stearate in a con
are suitable for our purpose are, for example, the
centration of .06% effectively broke a semi-stable
fatty sulfates, such as mono‘ lauryl, cetyl, stearyl,
etc., sulfate acids; or mono esters of sulfuric acid
_ obtained by treating with strong to moderately
strong sulfuric acid Various olefins or alcohols
such as the long chain olefins obtained in the
vapor phase cracking of wax at about 350‘°-560°
C., polymers obtained in the polymerization of
normally gaseous ole?ns with inorganic polyoxy
acids or Friedel-Crafts catalysts, fatty or naph
solutiz‘er emulsion; while in .08%‘ concentration
a stable emulsion remained. v p’
Example I
In the table below, effects of a number of repre
sentative surface-active ‘agents-are shown in a
monium acetate solution which when fresh had
thefollowingcomposition: .25 mol/liter of cupric
ions, 2.93 mols/liter of cuprous ions, 10.4 mols/liter
of ammonia, and 4.0 mols/liter of acetic acid,
plete separation was noted, and whether'or not
at the end of the settling time a rag was left at the
Samples of this spent solution were subjected to
'Other samples of the same solution were sub
an emulsion test in which they were agitated
with an equal amount by volume of tertiary o jected to a distillation test in which their rela
amylenes at a temperature of about 25° F. The
tive foaming tendencies were observed. Results
resulting emulsion was then allowed to settle and
were as follows:
Addition compound
cross-time in
mg./l00 cc.
None __________________________________________________________________________ _.
sulfate of higher secondary alcohol _______________________ __
Mildly positive.
Negative ______ __
Sodium lauryl sulfate ____________________________________________ __
Sodium sulfonate ethyl methyl oleoamide _______________________ ._
No improvement.
Sodium sulfonate ethyl oleoamidc _________________ ._
Sodium petroleum sulfonate _______________________ ._
Sodium hydrocarbon sulfonate ______________________ __
Very much improved.
Slightly improved.
Sodium alkyl aryl sulfonate ____ _._ _____ __
Much improved.
Dioctyl ester of sodium sulfo sucemate _______________ _.
Mildly improved.
Sodium sulfonate of complex stearyl alkyl compounds.
Sodium salt of green acids _______________________________________ _.
the time required for substantially complete sep-
We claim as our invention:
aration was noted and whether or not at the end 25
1. In a, process for treating a mixture com
of the settling a residual rag (large globules of
hydrocarbon surrounded by thin ?lms of solution)
Was left at the interface between the solvent
phase’ and the hydrocarbon phase. The results
were as follows:
Organic surface-active agent
Fresh solution ..................................................... ..
Spent solution _____________________________________________________ ..
prising predominately hydrocarbons with an
aqueous alkaline treating liquid to effect the sep
aration of components of said mixture which are
soluble in the .treatirvT liquid from components
which are not soluble therein, in which process
Gone. in‘
gin/100 cc.
time in
Vol. of
No foam.
Stable foam.
No foam.
I. Salts of organic acids:
A. Sulfonic acids—
Produced from transformer oil extract ___________________ _.
0 ____________________________________________ _.
Commercial petroleum sulfonates __________________ __
0 ____________________________________________ __
“Green acids” _____________________________________ __
Sodium amyl alkyl poly-ether sulfonate ___________ __
Dioetyl ester of sodium sulfo succinic acid _________ __
D0 _________________________________________________ __
B. Sulfuric ester 'acids—
. 1
. O1
No foam, refused to emulsify.
No foam.
Hydrolyzes rapidly.
No foam.
Glyceryl rieinoleyl sulfate (Turkey red oil) ______________ __
Do ____________________________________________ __
Do ____________________________________________ __
. 001
Alkyl sulfate-i-NazSOi ______________________________ _ _
Do __________________________________________________ __
. l
(C4H9)CH<O2H5>C2H4?HC2H4CH(C2H4)2 ______________ ._
. 01
. 1
Sodium alkyl sulfate ____________________________________ ._
0. Naphthenic acids-
Cyclic carboxylic acids __________________________________ _Do ______________________________________ __
Naphthenic acids (equiv. wt. 332) _________ _.
Do __________________________________________________ ._
. 01
D. Fatty acids
Larvic acid ______________________________________________ _Do ___________________________________________________ __
No foam.
Example 11
60 two phases are produced, a ?rst phase compris
ing predominately hydrocarbons and a second
The following table discloses the effects of a
phase. comprising predominately aqueous alka
number of representative surface-active salts
line treating liquid and at least a substantial por
covered by this invention when employed in a
tion of components of said mixture which are
solutizer solution having the following composi
soluble therein, in which process a relatively sta
ble dispersion of one phase in the other is pro
___________________________ __ 6
duced, the improvement comprising the method
of reducing the stability of such a dispersion
which comprises e?eoting said treatment in the
Samples of the solution containing various 70 presence of from about 0.001% to about 1% by
volume of said treating liquid of an organic sur
ones of the surface-active salts were subjected to
an emulsion test in which they were agitated with
face-active agent which forms a dispersion itself
a cracked gasoline under standardized conditions,
of particles at least as small as of colloidal di
and the resulting emulsion was then allowed to
mensions in said aqueous treating liquid, which is
settle. The time required for substantially com 75 substantially insoluble in said mixture and which
Potassium isobutyrate ____________ __ 1.5 normal
Potassium phenolate _____________ __ 1.0 normal
is a salt of a naphthenic acid having a molecu
fraction containing substantial proportions oi
lar weight between about 250 and 500.
2. The process of claim 1, wherein said mix
hydrocarbons with di?erent degrees of satura
ture is a gasoline distillate.
3. The process of claim 1, wherein said mix
ammonium acetate solution, whereby two phases
tion and unsaturation with an aqueous copper
are produced, a ?rst phase comprising predomi
ture contains a substantial proportion of 04 di
nately hydrocarbons of a higher degree of satu
ration and a second phase comprising predomi
4. The process of claim 1, wherein said treat
nately said aqueous solution and dissolved there
ing process is a liquid-liquid phase separation
in a substantial proportion of the hydrocarbons
10 of said fraction which have a higher degree of
5. The process of claim 1, wherein the treat
unsaturation, in which process a relatively sta
ing process is a vapor-liquid phase separation
ble dispersion of one phase in the other is pro
duced by the action of impurities formed as a
6. The process of claim 1, wherein said mix
result of reactions of unsaturates in said mixture
ture contains diole?ns and said alkaline treating 15 with each other and with oxygen, the method of
solution is an aqueous copper ammonium acetate
preventing such a dispersion which comprises ef
7. The process of claim 1, wherein the amount
of the said surface-active agent is between about
.001% and .1% by volume of said mixture.
8. The process of claim 1, wherein said sur
face-active agent is an alkali metal naphthe
9. The process of claim 1, wherein said dis
persion is a foam.
10. In a process for contacting a hydrocarbon
fecting said treating in the presence of from
about 0.001% to about 1% by volume of said
aqueous solution of an alkali metal salt of a
petroleum naphthenic acid dispersable in said
aqueous copper ammonium acetate solution, said
‘naphthenate having av molecular Weight be
tween about 250 and 500.
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