DE1642825B1 - Process for separating aqueous emulsions from organic liquids - Google Patents

Description

1 2

For separating parts that are difficult to separate from each other

mix up mutually insoluble liquids, with or less severe defects by either

For example, crude oil that is contaminated with salt water only has a specific effect on certain types of oil,

if one uses different me- dia in technology, they are therefore not universally applicable, or a particular

methods. In addition to simply letting it stand, heating 5 peaceful cleavage only with simultaneous heating

and spin, enable the application of electrical voltage. The latter is particularly a hindrance,

more recently, the addition of over- if the processing of crude oil is not an immediate

Surface-active substances are taking place more and more in significant proximity to the place of discovery. In extreme

tung won. Cases, especially when the outside temperature is up

From the large number of those proposed for this purpose approaching freezing point, the

Genetic substances have the following connection types because they are not broken

Found in practice: Emulsion the line pressure due to high viscosity

_T _ ,,,,, ",. ·. · ^ ₁ , j, increases considerably. Therefore come the one

I. Polyadducts from epoxies such as ethylene oxide and _{g ltem dne special importance to} the already

Propylene oxide m of the kind that on polypropylene _{- 15 ir} f in the _{immediate vicinity of the} drilling site - in the cold

Glycols with molecular weights from 500 to 3000, pre- _added _ _{enable cleavage} , which means that the

preferably 2000, ethylene oxide increasing the _{viscosity of the emu} t _{sion and thus the} delivery pressure

The final molar weight is added by 30 to 100% j _{der Lei k} j _d

USA -Patentschnft 2 674 619 and German Aus. _{Eg was} * £ _{found; that one is too extremely wif} . laid down i UlS 1 / y). _{20 kungsvol} i _{len and un} j _v ersal applicable splitters gell. Alkylphenol resins that can long in organic solvent, if one is soluble in the listed under III agents and their free hydroxyl products, which in the simplest case by reaction with alkylene oxides such groups subsequently 2 moles of polyether diol with 1 mol diisocyanate corresponds Mk Athylenoxyd and / or propylene oxide are reacted (III b), 1 mole of polyether diol by 1 mole of the ^w were. The alkylphenols required for this are replaced ² S compounds listed under II, ie the bifunctional monoalkylphenols with straight-chain substances listed under III b and II or I and II or branched alkyl groups with 1 to simultaneously react with diisocyanates.
24 carbon atoms in o- or p-position, whereby the invention thus provides a process in which smaller amounts of bis-alkylated phenols for separating aqueous emulsions can be present organically. To convert them into 3o liquids, preferably from emulsions made of resins, mainly formaldehyde or mineral oils with water or salt solutions, which are substances that under the selected reaction is characterized in that formaldehyde is given off under the steady-state conditions, but also the flowing Emulsion small amounts of um-acetaldehyde and higher aldehydes. The aldehyde settlement products from
amount is 0.9 to 2 mol, preferably 35 ...,. ,,., _ ..

1 mole for 1 phenol molecule. The enable it to go ^a> aliphatic and aromatic diisocyanates

follows in a known manner in the presence of acidic or ^ -

alkaline catalysts with and without additives b) adducts from mixtures of polyethylene glycol

indifferent solvent. kolen and hydrophobic polyalkylene glycols with

These resins are made by known processes * ° diisocyanates (III b)

oxalkylated, the amount of to or

using oxyalkylating agent once after the addition products of ethylene oxide to water

Length of the insoluble polyalkylene glycols (I) contained in the starting phenolic resin

Alkyl groups, on the other hand according to the own and M ^

shafts of the crude oil to be split (USA.- ⁴⁵ ^

Patents 2,499,368, 2,499,370, 2,524,889, ^c ) condensation products of bifunctional mono-

2,560,333 and 2,574,543). alkylphenols, the o- or p-position, straight or

branched alkyl groups with 1 to 24 carbon

III. Have reaction products from atoms, with aldehydes in a molar ratio

a) the polyadducts listed under I 50 0.5: 2, preferably 0.9 to 1.1, their free or hydroxyl groups reacted further with epoxides

b) Mixtures of water-soluble and water-insoluble were, with 2 to 20 moles of epoxy on one Licher polyalkylene glycols OH equivalent of the resin for the application or long (II),

c) Products which by simultaneous addition ⁵⁵

of monomeric ethylene oxide and higher added.

monomeric alkylene oxides of water or ^{New s} P ^{age zei} § ^s compared to the previously

Glycols give well-known products a number of advantages:
with aliphatic or aromatic diiso- _K They split very quickly, especially in the cold

c ^ anaten The implementation can be done directly or in ^6o <& ^zu ~ ^{10 C. u} f ^aar , ^mt f: Apart from the fact that

A 4. ■ Λ-tc ^ t- - ^ 1 _t 1 thereby the inlet pressure m the delivery lines

In the presence of indifferent solvents, ^,. ".? . _c , - ^ , ,,. , ^&

(■ German patent 1 197 082Ϊ ^{from the drilling site bls for} reconditioning considerably

(aeutscnes ratent 1 i ~ / uöz). _{If we come, the emulsion is} largely broken

_{genkt we come} ^ _{the emulsion} largely broken IV. products of, so that most of 65 water can be separated even at 20 ° C by reacting together at the collection of the substances listed under I and II with dicarboxylic. Demic acid or its anhydrides, such as diglycolic acid, only needs one and maleic anhydride to form for complete separation (USA.-Pa- lower volume of liquid to be heated, publications 3 202 614 and 3 202 615). which saves energy costs.

Furthermore, the effect of the new cleavers is largely independent of the mixing intensity of the respective Pump, with the help of which the splitters are injected into the flowing emulsion. Also stays with Overdosing the splitter leaves the draining water free of oil, which is the case with the resin splitters, for example mostly not the case.

It is also important that the effect of the new breakers is independent of the age of the emulsion, what especially for the subsequent splitting of those that have been delivered to refineries and those that have not yet been prescribed Oils with water content are important.

In the following tables the new splitters are compared with the known products.

A. Crude oil from southern Germany with a water content of 36%; Splitter input 20 g / t crude oil

product

temperature
⁰ C

% separated water 10 after minutes 30th 60 : 0 15th 14th 40 0 2 37 65 0 7th 25th 46 2 5 50 70 30th 15th 82 85 46

Re = residual emulsion water

in O

Pluronic (I)

Pluronic + diisocyanate (III a)

Resin splitter (II)

Pluronic + resin splitter + dicarboxylic acid (IV)

New splitter

50
50
50
50

50

16

11th

14th

B. Crude oil from Northern Germany with a water content of 50%; Splitter input 20 g / t crude oil

product

temperature
⁰ C

% separated water 10 after minutes 30th 60 : 0 15th 0 ₁ 0 0 0 3 0 0 0 2 7th 0 22nd 28 15th Q 64 72 40

Re = residual emulsion water

in ⁰ /.

Pluronic (I)

Pluronic -f- diisocyanate (III a)

Resin splitter (II)

Pluronic + resin splitter + dicarboxylic acid (IV)

New splitter

50
50
50
50

50

18th

15th

17th

The residual emulsion water is determined in such a way that 100 ml of the spalter were added Crude oil sample can be centrifuged after 1 hour standing in a water bath at 50 ° C, the oil phase pipetted off and the water content is determined by circling with xylene.

As starting materials for the production of the new splitter serve once diisocyanates such. B. hexamethylene diisocyanate, Tolylene 2,4- and 2,6-diisocyanate, 1,4- and 1,5-naphthalene diisocyanate, diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate; Triisocyanates are only suitable if one of the three isocyanate groups is considerably less is more reactive than the others.

Instead of the diisocyanates just mentioned, it is also possible to use products which, in their partial Reaction with bifunctional compounds containing active hydrogen atoms are formed, e.g. when combining 2 moles of diisocyanate with 1 mole of a diol such as. B. Glycol.

Those compounds are also suitable which, under the given test conditions, are isocyanate groups release, thus reacting like Isocynate.

The second group of starting materials are the polyadducts of epoxides listed under I, the arise in that one of polypropylene glycols with molecular weights of 500 to 3000, preferably 2000, ethylene oxide deposits with an increase in the final molecular weight by 30 to 100% and the under III b reaction products described from mixtures of water-soluble and water-insoluble polyalkylene glycols with aliphatic and aromatic diisocyanates.

The third group of starting materials are the alkylphenol resins listed under II, which consist of bifunctional Monoalkylphenols with straight or branched alkyl groups with 1 to 24 carbon atoms in o- or p-position by reaction with aldehydes in a molar ratio of phenol to aldehyde such as 0.9 to 2: 1 and subsequent alkoxylation of the resin formed by known processes arise, 2 to 20 moles of epoxy per OH equivalent of the resin are used.

In the manufacturing process, 2 moles of substances I or III b are mixed with 0.75 moles to 1.3 moles of substances II and reacted together with 0.9 to 1.75 moles of diisocyanate, in the presence or absence of inert diluents such as xylene. The same can be found in the final product remain or are distilled off. However, one becomes the extremely reactive diisocyanate in everyone Dilute the case with an equal amount of an inert solvent. Catalysts such as organic Tin compounds, tertiary amines and the like can be present during the reaction. The reaction temperatures are above 100 ° C, mostly 140 to 200 ° C. Should components I and II of Their preparation from too high an alkali content, they are before the reaction with diisocyanate by suitable acids, such as. B. hydrochloric acid or acetic acid to neutralize. A resulting salary of water is removed before the reaction by means of vacuum or azeotropic distillation.

The new surface-active products produced in this way are then, if desired, with other known surfactants, such as. B. Petrol sulfonates and the like., Mixed and come pure or diluted with water, methanol and solvent naphtha or distributed in crude oil for practical use, by adding 200 to 2 ppm, preferably 50

up to 5 ppm of the active substance on the liquid mixture to be split, at the place of origin - i.e. at the Probe -, also during processing or shortly before final processing (in the refinery), if necessary with the use of an electrical splitting system, can act.

The production of the new splitter can be carried out continuously as discontinuous.

For example

Polypropylene glycol with an average molecular weight of about 2000 is known in The presence of alkaline catalysts reacted with so much ethylene oxide that an adduct with one average molecular weight of about 3000 is formed (I).

p-Nonylp_henol is in a known manner in the presence of caustic soda with a little more than the equimolecular Amount of formaldehyde reacted and the water formed by. distillation freed. This gives a brown resin which is soluble in white spirit and has a molecular weight that is about 5 times the unit of nonylphenol-formaldehyde. Then this resin is under renewed Addition of alkali treated with so much ethylene oxide that a resin mole unit, i.e. H. on a phenolic OH group, 5 moles of ethylene oxide come. The solid, oxyethylated resin has an OH number of about 125 (II).

3000 parts by weight of the product I is mixed with 235 parts by weight of the product and II are mixed at 140 to 170 ⁰ C within one hour with 125 parts by weight of a commercial 2,4- and 2,6-toluene diisocyanate, dry with 200 parts by volume of benzene, the reaction brought. A brown, syrupy, surface-active product which is soluble in many solvents and in water is obtained.

20 parts by weight of this product are mixed with 1,000,000 parts by weight of about 35% salt water containing crude oil from the South American area mixed well and left to stand at room temperature. After a relatively short time, a practically water- and salt-free separates out for further processing suitable oil.

Example 2

A mixed adduct of propylene oxide and butylene oxide with an average molecular weight of 1500, the already contains sufficient alkali from its production, it is reacted with so much ethylene oxide until the final molecular weight is about 3000 (I).

A butylphenol resin is prepared from 1 mole of tertiary butylphenol as described in Example 1 and 1.05 mol of formaldehyde in the presence of phosphoric acid and then initially with 2 moles of propylene oxide, then reacted with 3 moles of ethylene oxide (II).

1280 parts by weight of the product I and 83 parts by weight of the product II are in the same weight of solvent naphtha (70% xylene, 25 ° / ₀ cumene, 5% toluene; to 160 ⁰ C Kp 9O ° / o.) And azeotropically dewatered. Then 34 parts by weight of hexamethylene diisocyanate are slowly and evenly run into the reaction vessel at reflux temperature, with quantitative conversion taking place. The final concentration is adjusted to exactly 50% by adding methanol.

50 ppm of this solution at an external temperature of - 10 ⁰ C metered continuously directly on the probe a Southern German oil field in the delivery line. The initial pressure, which was previously an average of 45 atmospheres for oil splitters of type 1 and 2, drops immediately to around 20 atmospheres, which is due to the splitting which started immediately. "The final separation then takes place in the" treaters the processing plant at about 20 to 6O ⁰ C instead and provides a type fairly, mailable crude oil. The separated water is perfect and can be pumped back into the field as pressurized water or drained into receiving waters.

Example 3

1 mole of a polypropylene glycol 2000 and 2 moles of a polyethylene glycol 1000 are with about 2 moles Tolylene diisocyanate reacted in a known manner in the presence of xylene (III b).

A commercially available, so-called oil-soluble alkylphenol resin is reacted with 80% of its weight with ethylene oxide ^{at 130 to 150 ° C. after adding 1% sodium methylate.} The interfacial tension of a 1% solution of this product in xylene versus 10% saline solution is 2 (II).

2000 parts by weight of product III b are homogeneously melted with 125 parts by weight of product II and 50 to 60 parts by weight of tolylene diisocyanate are gradually added at 150 to 170 ^° C. with very good stirring and kept at the same temperature for a further 30 minutes.

Before it is used, the product obtained is made up of three times its weight in adduct I. Example 1 mixed.

A crude oil delivered to a North German refinery from the South Arabian region did not yet have it the salt content prescribed for the distillation. The crude oil was washed with fresh water that was about Contains 12 ppm splitter, based on oil, and delivered without additional activation of the existing electrical system Splitting plant a flawless, processable crude oil.

Claims (5)

Patent claims: 1. A method for separating aqueous emulsions of organic liquids, characterized in that that the stationary or flowing emulsion small amounts of reaction products the end a) diisocyanates with b) Adducts from mixtures of polyethylene glycols and hydrophobic polyalkylene glycols with diisocyanates (III b) or Addition products of ethylene oxide to water-insoluble polyalkylene glycols (I)
and c) Condensation products of bifunctional monoalkylphenols, the o- and p-positions, straight or have branched alkyl groups having 1 to 24 carbon atoms with aldehydes in a molar ratio of 0.5: 2, preferably 0.9 to 1.1, with their free hydroxyl groups Epoxies were reacted further, with 2 to 20 moles of epoxy per OH equivalent of the resin are used, can be added. 2. The method according to claim 1, characterized in that the application concentration 200 to 2 ppm, based on the emulsion. 3. The method according to claim 1 and 2, characterized in that for the production of the splitter 2 moles of component b) and 0.5 to 1.3 moles of component c) with 0.9 to 1.75 moles of component a) be brought to reaction. 4. The method according to claim 1, 2 and 3, characterized in that the new breakers in solvents dissolved or homogeneously suspended for use. 5. The method according to claim 1 to 4, characterized in that the new splitter with others Surface-active substances get used together. 109 527/334