Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ 7!7~r
The present invention relates to a process for the
breaking of water-in-oil emulsions which are the oily
phase separated off from a previously broken oil-in-water
emulsion. In the following text, the breaking of the oil-
in-water emulsion is also called primary breaking and the
~reaking of the resulting oily phase is called secondary
breaking.
Various processes and corresponding organic and inorganic
breakers are known for primary breaking of oil-in-water
emulsions. A water-soluble polymer is often employed for
the primary breaking, cationic products in general being
preferable to anionic and nonionic products.
Examples of primary breakers are:
synthetic polymers based on acrylamide, pure polyacryl-
amide being nonionic, copolymers of acrylamide and
acrylate being anionic and copolymers of acrylamide and
cationic monomers or oligomers being cationic (see, for
example, US-A 3,585,148, US-A 4,699,951, DE-A 2,345,922
and DE-A 2,926,103), and furthermore
synthetic polymers based on polyamines and polyamido-
amines, as well as quaternised polyamines and quaternised
polyamidoamines (see, for example, DE-A 2,262,284, JA-OS
(Japanese Published Specification) 20,929-66, US-A
3,915,904, DE-A 2,638,516, US-A 4,287,331, French Patent
Specification 1,449,204, US-A 4,575,527, DE-A 2,156,215
Le A 27 853 - 1 -
,f,
and DE-A 2,351,754), and furthermore
homopolymers of dimethyldiallylammonium chloride, also
called DADMAC (see, for example, EP-A 0,186,029) and
inorganic breakers, such as inorganic metal salts, for
example of magnesium, sodium, calcium, iron, silicon,
aluminium and cerium, which can be employed in the form
of hydroxides, oxides, chlorides or sulphates. In
accordance with the Schulze-Hardy rule, di- and trivalent
salts are preferably employed here (see Kirk-Othmer,
Encyclopedia of Chemical rrechnology, 3rd edition, Volume
10, 489, New York 1980).
In the primary breaking, the oily phase is as a rule
obtained in the form of a flotation product which creams
on the aqueous phase And i5 in general a water-in-oil
emulsion. This can be removed mechanically from the
surface of the liquid in a simple manner and then passed
for secondary breaking.
A secondary breaking is in general advantageous if the
oily phase separated off from the waste oil-in-water
emulsion is to be disposed of, for example by working up,
dumping or burning. It is then advantageous if this oily
phase contains as little water as possible.
For breaking of crude oil emulsions which are water-in-
oil emulsions, it is known that block polymers of
ethylene oxide and/or 1,2-propylene oxide (see US-A
Le A 27 853 - 2 -
~ ~ ~J ~ J ~1
2,964,478)l oxyalkylated phenolic resins (see US-A
2,499,370 and US-A 2,499,368) and block polymers or
copolymers of ethylene oxide and 1,2-propylene oxide
crosslinked with diisocyanates, dicarboxylic acids,
formaldehyd~ and/or diglycidyl ethers (see EP-A 55,433
and 55,434 and ~S-A 4,029,708) and polyether-urethanes
(see DE-A 3,706,151) can be employed as breakers.
The secondary breaking to be carried out according to the
invention, that is to say the breaking of a water-in-oil
emulsion which can be the oily phase from the breaking of
an oil-in-water emulsion, canno~ be compared with the
breaking of a crude oil emulsion, because the water-in-
oil emulsions which arise in crude oil production are
highly stabilised by specific natural emulsifiers. The
breakers employed for the breaking of crude oil emulsions
have been designed specifically for this breaking. In
the emulsion breaking according to the invention, the
emulsions to be broken contain no stabilisers or
completely different stabilisers from crude oil
emulsions.
Breakers which are known for the breaking of crude oil
emulsions therefore cannot be applied to secondary
breaking of oily phases which originate from breaking of
an oil-in-water emulsion.
A process has now been found for the breaking of water-
in-oil emulsions which have been obtained from the
breaking of oil-in-water emulsions, which is
Le A 27 853 - 3 -
characterised in that polymers and/or oligomers of
ethylene oxide and~or 1,2-propylene oxide, oxyalkylated
phenolic resins, block polymers or copolymers of ethylene
oxide and l,2-propylene oxide crosslinked with
diisocyanates, dicarboxylic acids, formaldehyde and~or
diglycidyl ethers, polyether-urethanes and~or
alkylbenzenesulphonic acid salts are employed as the
breakers.
Pol~mers of e~hylene oxide and/or 1,2-propylene oxide
which are sui~able for the process according to the
invention can be obtained, for example, by polyalkoxy-
lation of lower alcohols, such as methanol, ethanol,
propanols, butanols, pentanols or hexanols, with ethylene
oxide and/or 1,2-propylene oxide. Possible alcohols here
are also di- and polyols, for example propanediols,
butanediols, neopentylglycol, other pentanediols, adipol,
hexanediols, cyclohexanediols, 1,4-dihydroxymethylcyclo-
hexane, perhydrobisphenol A, glycerol, trimethylolethane,
trimethylolpropane, other hexanetriols and pentaeryth-
ritol. Lower amines, for example ethylenediamine anddiethylenetriamine, can also be polyoxyalkylated with
ethylene oxicle and/or 1,2-propylene oxide in order to
obtain polymers which are suitable for the present
invention. Both block polymers and polymers having a
random distribution of different oxyalkyl groups, so-
called copolymers, or also mixed forms of these two
possibilities, can be used according to the invention.
Block polymexs of ethylene oxide and 1,2-propylene oxide
and those products in which alcohols are first reacted
Le A 27 853 - 4 -
with a mixture of propylene oxide and 70 to 90% by weight
of the total amount of the ethylene oxide to give copoly-
mers, and the remaining 10 to 30~ by weight o the
ethylene oxide is then introduced, so that a polyether
which contains practically only primary OH end groups is
formed are preferred. Polymers of ethylene oxide and 1,2-
propylene oxide which contain 40 to 60~ by weight of
ethylene, based on the sum of ethylene oxide + 1,2-
propylene oxide, are preferred. Particularly preferred
polyethers are built up from the same amounts by weight
of ethylene oxide and 1,2-propylene oxide. Polyethers
having molecular weights of 600 to 6000, particularly
preferably those having molecular weights of 1000 to
5000, are furthermore preferred.
Oxyalkylated phenolic resins which are suitable for the
process according to the invention can be obtained, for
example, by condensation of alkylphenols with formalde-
hyde, formalin solution or paraformaldehyde and subse-
quent alkoxylation.
Block polymers or copolymers of ethylene oxide and/or
1,2-propylene oxide which ar~ crosslinked with diisocyan-
ates, dicarboxylic acids, formaldehyde and/or diglycidyl
ethers and are suitable for the process according to the
invention can be obtained, for example, if a difunctional
polyether consisting of, for example, 30 to 90 parts by
weight of 1,2-propylene oxide and 70 to 10 parts by
weight of ethylene oxide and having a molecular weight of
2000 to 20,000 is reacted with a bifunctional isocyanate,
Le A 27 853 - 5 ~
a bifunctional carboxylic acid, formaldehyde and/or a
bifunctionaL glycidyl ether. Examples of suitable diiso-
cyanates are hexamethylene diisocyanate, cyclohexane 1,4-
diisocyanate, toluylene 2,4- and 2,6-diisocyanate and
mixtures thereof, 1-isocyanatomethyl-5-isocyanato-1,3,3-
trimethylcyclohexane, 2,2,4- and 2,4,4-trLmethylhexa-
methylene 1,6-diisocyanate, naphthalené 1,5-diisocyanate,
cyclopentylene 1,3-diisocyanate, m- and p-phenylene
diisocyanate, xylylene 1,3- and 1,4-diisocyanate, 3,3'-
dimethyl-diphenylmethane 4,4'-diisocyanate, diphenyl-
methane 4,4'-diisocyanate, 3,3'-dimethyl-biphenylene
4,4'-diisocyanate, biphenylene 4,4'-diisocyanate, durene
diisocyanate, 1-phenoxy-phenylene 2,4'-diisocyanate, 1-
tert.-butyl-phenylene 2,4-diisocyanate, methylene-bis-
cyclohexyl 4,4'-diisocyanate r l-chloro-phenylene 2,4-
diisocyanate and diphenyl ether 4,4'-diisocyanate.
Examples of suitable bisglycidyl ethers are bisglycidyl
ethers of bisphenol A, reaction products of bisphenol A
and epichlorohydrin, reaction products of epichlorohydrin
and aniline and reaction products of perhydrophthalic
acid with epichlorohydrin. Examples of suitable difunc-
tional carboxylic acids are oxalic acid, malonic acidr
succinic acid, glutaric acidr adipic acidr pimelic acidr
suberic acidr maleic acidr fumaric acid and higher
saturated or unsaturated dicarboxylic acids.
Examples of crosslinked block polymers or copolymers of
ethylene oxide and/or 1 r 2-propylene oxide which are
suitable for the process according to the invention are
linked and amine-modified polyalkylene oxides of the
Le A 27 853 - 6 -
2 ~
general formula ~I)
NH-CHR-~CH2)x-CHR-t-OCllR-(CH2)x-CHR-]y~(OCHR~CHR)y~O~Q~A
NH-C1~R-(CH2)x-CHR-[-OCKR-tCHz)x-CHR-]y~(OCHR~CHR)y~O~O~A
(I)
in which
each R independently denotes hydrogen or a Cl-C20-alkyl
radical,
each x independently denotes zero or an inte~er from 1
to 12,
each y independently denotes zero or an integer from 1
to 120,
0 each Q independently denotes a C6-C1B-arylene, C7-Cl~-
aralkylene or C2~Cl8-alkylene ~roup,
each A independently denotes hydrogen, hydroxyl or a
radical of the formula (II)
-(OCHR-CHR)y~[-OCHR-(CH2)x~CHR~~y~OCHR~(CH2)x~CHR~NH2
(II)
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2~-i; 7 ?r~
where R, x and Y are as defined above, and
M denotes the radical of a diisocyanate, a bisepoxide,
a dicarboxylic acid, a dicarboxylic acid dihalide,
a biscarboxylic acid anhydride, a diester or a
dihalogen compound, after the two reactive groups in
each case have reacted with an amine hydrogen atom.
Preferred crosslinked block polymers and/or copolymers of
ethylene oxide and/or 1,2-propylene oxide can be obtained
by reacting monofunctional polymers of ethylene oxide
and/or 1,2-propylene oxide with diisocyanates, bisgly-
cidyl ethers or dicarboxylic acids, for example ~hose
described above, and then reacting the products with a
polyalkylenepolyamine.
Examples of polyether-urethanes which are suitable for
the process according to the invention are urea-modified
polyether-urethanes of thP formula (III)
NH-C0-NH-R3-t-NH-C0-0-(CHR6-CHR70)X-(CHR8-CHR9-o)y~RlO~m
IRl
N-C0-NH-R4-~-NH-C0-0-(CHR6-CHR70)x-(CHR8-CHR9-O)y~RlO]m
Rl2
NH-CO-NH-R5-~-NH-CO-O-(CHR6-CHR70)x-(CHR8-CHR9-O)y~RlO]m
(III)
Le A 27 853 - 8 -
7 . J
in which
Rl and R2 independently of one another denote C2-C14-
cycloalkylene,
R3, R4 and R5 independently of one another denote option-
ally substituted alkylene, cycloalkylene or
arylene,
R6, R~, R~ and Rg independently of one another denotehydrogen or Cl-C20-alkyl,
Rlo denotes C1-Cl8-alkyl, C6-Cl8-aryl, C7-C1a-aralkyl or
C2-C18-alkenyl and
n represents a number from O to 50,
m represents a number from 1 to 4,
x represents a number from 5 to 100 and
y represents a number from O to 100.
Preferred polyether-urethanes are formed by reaction of
polymers of ethylene oxide and/or 1,2-propylene oxide,
which have been obtained as described above, with a
bifunctional isocyanate, such as is described above for
the prepara~ion of crosslinked block polymers or copoly-
mers, and a polyalkylenepolyamine.
Le A 27 853 - 9 -
~" V,; ~ ,: " ~ !,
Polyurea-modified polyether-polyurethanes which have been
prepared, for example, from ethylenedi~mine, diethylene-
triamine, triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, polyethyleneimine, 1,2- or 1,3-
propylenediamine, dipropylenetriamine, tripropylene-
tetramine, butylenediamine, hexamethylenediamine, 2,5-
diamino-2,5-dimethylhexane, 2,2,4- or 2,4,4-trimethyl-
1,6-hexanediamine,cyclohexanediamine,isophoronediamine,
hydrogenated toluylenediamines and hydrogenated diamino-
diphenylmethanes can also be employed.
Polyamines which are trifunctional or more than trifunc-
tional are preferred here. Diethylenetriamine, triethyl-
enetetramine, tetraethylenepentamine and pentaethylene-
hexamine are particularly preferred.
Industrial distillation xesidues from the preparation of
the oligoethyleneamines mentioned are also particularly
suitable for the preparation of polyurea-modified poly-
urethanes which can be used according to the invention.
These residues then additionally contain branched and/or
cyclic polyalkylenepolyamines.
Alkylbenzenesulphonic acid salts which are suitable for
the process according to the invention are, for example,
salts of alkylbenzenesulphonic acids and alkylnaphthal-
enesulphonic acids. Salts of dodecylbenzenesulphonic acid
are particularly preferred.
It is possible and sometimes advantageous to use a
Le A 27 853 - 10 -
~ ~ ~ 7 ~ i 3
mixture of 2 or more of the breakers to be employed
according to the invention.
The breakers to be used according to the invention can
be employed, for example, in an amount of 5 to 18,000
ppm, based on the emulsion to be broken. This amount is
preferably 10 to 10,000 ppm.
The water-in-oil emulsion to be broken secondarily
according to the invention, which is an oily phase
originating from the primary breaking of an oil-in-water
emulsion, can originate from the most divers~ oil-in-
water emulsions, for example from effluents containing
fat and/or oil or from used oil-in-water emulsions.
Examples which may be mentioned are: mineral oil-based
and semi-synthetic cooling, lubricating and rolling oil
emulsions, effluents from tank cleaning, bilge water,
slop oils, oil-containing wash liquors, degreasing baths
to be disposed of, paintshop effluents, oil-containing
condensates and effluents from the processing of animal
and plant products, from breweries and distilleries, from
metalworking and metal processing plants, from membrane
proces~es, for example retention products from ultra-
filtrations and reverse osmosis processes, and from
flotation processes.
The process according to the invention can be carried
out, for example, at temperatures in the range from 0 to
100C. It is preferably carried out in the range from 10
to 80C.
Le A 27 853
: ~I i, ., i , , ;
The process according to the inven~ion allows substantial
dehydration, by secondary breaking, of oily phases which
have been obtained from the breaking of oil-in-water
emulsions. As a rule, 60 to 90% by weight of the water
contained in the oily phases can be removed in the manner
according to the invention. Oily phases treated in this
way can be ~orked up and burned more easily and dumped in
a better manner than the oily phases which still have a
relatively high water content, containing, for example,
20 to 80% by weight of water, which originate directly
from the breaking of oil-in-water emulsions.
Examples
The following secondary breakers were used in the
examples:
Ethylene oxide/l 2-propylene oxide polymers
Al
A polyether having an OH number of 28 was obtained by
alkoxylation of trimethylolpropane (as the starting
substance) with initially 80 parts by weight of propylene
oxide and then 20 parts by weight of ethylene oxide. The
product was adjusted to an active compound content of 45%
by weight with toluene. A low-viscosity, almost colour-
less clear solution was obtained.
A2
A polyether having an OH number of 47 was obtained by
Le A 27 853 - 12 -
alkoxylation of ethylenediamine with initially 88 parts
by weight of propylene oxide and then 12 parts by weight
of ethylene oxide. The product was ad~usted to an active
compound content of 45% by weight with toluene. A low-
viscosity, almost colourless clear solution was obtained.
Oxyalk~lated phenolic resins
Bl
220 parts by weight of nonylphenol and 37 parts by wei.ghtof aqueous formaldehyde solution were heated and the
mixture was reacted with 4.5 parts by weight of 56%
strength sodium hydroxide solution to give a base resin,
the water formed being distilled off. 1.4 parts by weight
of powdered KOH were then added to 103 parts by weight of
the base resin, and the mixture was heated to 148C and
reacted with 78 parts by weight of ethylene oxide. After
cooling, the product was rendered neutral with 3.5 parts
by weight of acetic acid.
The resulting product was adjusted to an active compound
content of 45~ by weight with toluene. A clear, slightly
yellowish solution was obtained.
Crosslinked PolYmers of ethylene oxide and 1 2-PropYlene
oxide
C1
36 parts by weight of a bifunctional polyether prepared
as described under A2 were reacted with 0 8 part by
Le A 27 853 - 13 -
r~
weight of potassium tert.-butylate and 1.56 parts by weight
of toluylene diisocyanate at 1309C. After subsequ~nt
neutralisation with acetic acid and filtration, the
product was adjusted to an active compound content of 45%
by weight with toluene.
C2
The procedure was as for Cl, but instead of toluylene
diisocyanate, 1.52 parts by weight of the bisglycidyl
ether of bisphenol A were reacted. After subsequent
neutralisation and filtration, the product was adjusted
to an active compound content of 45% by weight with
toluene.
Crosslinked block polymers or copol~mers of ethylene
oxide and/or 1 2-propvlene oxide
Dl
Two different solutions were added dropwise to 51.6 parts
by weight of toluene:
Solution 1: 0.035 part by weight of toluylene
diisocyanate in 22 parts by weight of toluene
0 Solution 2: 7.6 parts by weight of aminopolyether, which
was an amination product of a polypropylene
oxide which had been started from tri-
methylolpropane and had an OH number of 32,
in 68.4 parts of toluene.
Le A 27 853 14 -
The solutions were simultaneously added dropwise at the
same rate at a temperature in the range from 0 to 5C.
The mixture was then allowed to after-react at room
temperature for 2 hours. A pale yellow liquid was
obtained.
Polyether-urethar,es
E1
15.7 parts by weight of toluylene diisocyanate and
0.02 part by weight of dibutyltin dilaurate were added to
a solution of 235.9 parts by weight of a polyether which
had an OH number of 21.4 and had been prepare~ by reac-
tion of butanol with equal amounts by weight of ethylene
oxide and propylene oxide, and the mixture was stirred at
50C until the polyether had reacted completely. This was
checked via the isocyanate number. 3 parts by weight of
diethylenetriamine were then added at 50C and the
mixture was allowed to after-react at 30C for 8 hours.
A pale yellow liquid was obtained.
Alkylbenzenesulphonic acid salts
F1
52 parts by weight of dodecylbenzenesulphonic acid,
31 parts by weight of xylene and 10 parts by weight of
butyldiglycol were brought together at 30~C, and 7 parts
by weight of diethylenetriamine were added dropwise to
this mixture. The product had a yellowish coloration.
Le A 27 853 - 15 -
~ r~
Example l
An effluent originating from car production which was an
oil-in-water emulsion was subjected to primary breaking
by addition of 0.1~ by weight of a polyamidoamine. The
oily phase obtained by this oper~tion, which still
contained 40~ by weight of water, was broken at room
temperature usin~ 0.9% by weight of a secondary breaker.
The secondary breaker consisted of a mixture of Al, Bl
and C1 in a weight ratio of 1.2:2:2 Af~er 2~4/8/16
hours, 16~20/35/50% by weight of the water present in the
oily phase removed had been separated off. A blank
sample, that is to say a sample of the oily phase left to
stand without addition of a secondary breaker, showed no
water separated off after 16 hours.
Example 2
An effluent oxiginating from car production which was an
oil-in-water emulsion was subjected to primary breaking
with 0.09% by weight of a polyamidoamine. The resulting
oily phase, which still contained 44~ by weight of water,
was broken at room temperature using various dosages of
various secondary breakers. The results can be seen from
Table 1. A blank sample, that is to say a sample of the
oily phase removed left to stand without addition of a
secondary breaker, showed no water separated off after
16 hours.
Le A 27 853 - 16 -
2 ~ . . J ~ j
o
-l o o ~ ~
~2
~p
-
w a
o ~ ~ o c~
r~
a) --
~ u~ o o~ ~ o ~
c)
h ~1
U~
. U~ o~ o o o
O ~`1 ~ ~I N t~l
b
.
U~
I~ ~P .
a -- o o o o o
s
u~
a) --
~ a
x
o .,~
D
_I 0 a~ ~ _~
. O ~ + .... + .
.4 O ~ ~ ~ C~
~ O ~r~ O
E~ u~ -- 3 .~
Le A 27_ 853 - 17 -
6; ~ , J,
Example 3
The procedure was as in Example 2, but partly with other
dosages and the secondary breaking was carried
out at a tempera~ure of 60C. The results obtained can be
S seen from Table 2. A blank sample~ that is to say a
sample of the oily phase left to stand without addition
of a secondary breaker, showed no water separated off
afte~ l hour.
Le A 27 853 - 18 -
f'J ~ 1 "" ~
O D~
~I
S~ ~
a
O
O
.C
h ~
d O O~ O
~3:
.~
~ Q
Ul
O o`P
-- o o o
.C
~q
,~
X
.,1 ~
.Y ~ ~o
~ O r
a)
h O O
.4 U~ .~1
~ U ~
a) c~ _l
a
I ~ O .C ~ U~
O ~ + .... + .
rC U ~ ~
~ ~1 ,~ . ~
~ u~ -- 3 ~ m -~
Le A 27 853 - 19 -
[~
Example 4
An effluent originating from car production which was an
oil-in-water emulsion was subjected to primary breaking
with 0.2% by weight of a polyamine. The oily phase
obtained by this procedure, which still contained 52% by
weight of water, was broken at 80C using ~arious
secondary breakers. The results can be seen from Table
3. A blank sample, that is to say a sample of the oily
phase left to stand without addition of a secondary
~reaker, showed no water separated off after 2 hours.
Table 3
Secondary breaker Dosage Water separated off
(in the case of (% by after 2 hours
mixtures, the weight weight) (% by weight of the
ratio is stated~ water present)
. .
B1 1 19.2
B1 + F1 1 67.3
1.5:3.5
F1 1 38.5
Exam~le 5
An effluent originating from steel production which was
an oil-in-water emulsion w~s subjected to primary
breaking with 0.15% by weight of a polyamine. The oily
phase obtained by this procedure, which still contained
Le A 27 853 - 20 -
60~ by weight of water, was broken at 60C using in each
case 0.5% by weight of various secondary breakers. The
results can be seen from Table 4. A blank sample, that is
to say a sample of the oily phase left to stand without
addition of a secondary breaker, showed no water
separated off after 2 hours.
Table 4
Secondary breaker Water separated off after x
(in the case of hours (% by weight of the water
10mixtures, the weight present)
ratio is stated) x = 1 x = 1.5 x = 2
Bl 0 10 60
A1 0
Bl + F1 10 20 50
1.5:3.5
Bl + Fl 25 30 40
1.5:7.0
Example 6
20 An effluent originating from steel production which was
an oil-in-water emulsion was sub~ected to primary
breaking with 0.18% by weight of a polyamidoamine. The
oily phase obtained by this procedure, which still
contained 72% by weight of water, was broken at room
temperatuxe using in each case l.0~ by weight of various
secondary breakers. The results can be seen in Table 5.
Le ~ 2Z 853 - 21 -
! ' ? ~
A blank sample, that is to say a sample of the oily phase
left to stand without addition of a secondary breaXer,
showed no water separated off after 14 hours.
Table 5
Secondary breaker ~ater separated off after x
(in the case of hours (% by weight of the water
mixtures, the weight present)
ratio is stated) x = 1 x = 14
A1 59 60
B1 72 76
Al + Fl 83 94
1 : 1 .
B1 + Fl 72 90
1:2.5
~xample 7
An oil-in-water waste emulsion from the field of waste
oil treatment was subjected to primary breaking with 0.4%
by weight of a polyamine. The oily phase obtained by this
procedure, which still contained 72% by weight of water,
was broken at 40C using 1.0% by weight of various
secondary breakers. The results can be seen from Table
6.
Le A 27 ~53 - 22 -
" ~
Table 6
Secondary breaker Water separated off after x
hours (% by weight of the water
present)
S x = 1x = 3x = 5x = 12
_ _ _ _ . _
Ai 11 18 21 25
A2 11 65 71 83
C2 0 0 60 60
Example 8
The procedure was as in Example 4, but the secondary
breakers employed were types Cl, Dl and El. The results
can be seen from Table 7.
Table 7
Secondary breaker Water separated off after x
hours (% by weight of the water
pres~nt)
x = 1 x = 3 x = 5 x = 12
Cl 4 7 9 10
Dl 2 6 13 16
E1 5 11 20 25
Le A 27 8S3 ~ 23 -
