DE1495827A1 - Process for breaking emulsions - Google Patents

Description

FARBWERKE HOECHST AG. Gendorf, July 23, 1964

former Meiater Luoius 4 Brüning Dr.Br/fc· Gd 1353

description to the

Patent application

"Procedure for splitting emulsions"

DBP 1 127 082 (Example 4) states that polyadducts which are formed in the reaction of a mixture of polyethylene glycol and small amounts of polypropylene glycol and diisocyanates are able to split crude oil emulsions if they are given a 0.5 Stirred #igen alcoholic solution of the adduct and 2 hours at 80 ⁰ C is left. The ratio of polyethylene glycol to polypropylene glycol in the Auaganga material is far on the side of the polyethylene glycol, for example 27 parts of polyethylene glycol and 1 part of polypropylene glycol.

Products of this type cannot be used in all cases to produce emulsions split satisfactorily.

It has now been found that a more rapid cleavage occurs at the same time Lower temperatures in a wide variety of crude oils are achieved by using the polyadducts in the production of the polyadducts instead of the cited patent specified larger excess of hydrophilic component selects ratios in which these to the hydrophobic Component (e.g. polypropylene glycol) in terms of quantity within the limits 2i1 bi3 is 1: 2, preferably in the ratio lil. In doing so, it expands at the same time as unnecessary to start from special high molecular weight polyethylene glycols (MW 10,000-20,000), but it is sufficient Polyethylene glycols with molecular weights from 500 to 10,000.

AIa further starting materials for the production of such polyadducts can use the addition products known under the name "Pluronioa" of ethylene oxide to water-insoluble polyglycols, especially poly-

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propylene glycol serve. It should be noted that the "Pluronioi" alone are already splitters, whereas the aforementioned Gemieohe from water-soluble and water-insoluble polyglycols as well as di Individual components have no noteworthy splitting effect on emulsions exercise. Instead of the addition products of ethylene oxide to water-insoluble polyglycols, compounds ala starting material can also be used those made of polytetrahydrofuran and similar polymers are used arise through the addition of ethylene oxide in a known manner.

Finally, ala Auagangamaterialien for the tjmaatz with Di-leooyanaten also so-called. ^M Heterio Polymers "are possible, compounds which are formed by the joint addition of ethylene oxide and higher alkylene oxides - preferably propylene oxide - to water or glycols. They consist of a polyether chain, which in the Weohael contains ethylene oxide and propylene oxide units.

The above-described Auaganga materials are treated in a manner known per se with di-isocyanates (or compounds which are able to react under the reaction conditions such as di-isocyanates), e.g. Hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate etc., briefly with all isocyanates that are suitable for the preparation of the so-called polyurethanes, reacted with Aujeohlusa of water. Included can be carried out in the presence or absence of inert solvents and the reaction, which itself proceeds very quickly, is caused by addition accelerated by catalysts.

The quantities of substances to be reacted can vary within wide limits. When 1 mole of a diol or the equivalent amount of one Diol-Gemiuches is brought together with 1 mole of a di-isooyanate » should a high-molecular substance arise) in practice, however, this state is not achieved due to chain-breaking side reactions. An excess of diisocyanate over the ratio 1: 1 is sioh possible, but inexpedient because of the free isoyanate groups that are inevitably remaining in the adduct.

Ei therefore recommends rather working with an excess of diol or diol mixture. In many cases the ratio has been 4-5 moles Diol to 3-4 moles of di-iaooyanate has proven particularly effective.

The manufacture of the new splitters is not the subject of the invention.

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The finished products are conveniently in solvents such as Xylene, alcohol, or even water, dissolved or homogeneously suspended, unless this already happens during manufacture.

To separate emulsions, the procedure is that the products described above are added continuously or discontinuously in amounts of 5-50 ppm of active substance, based on the emulsion in dissolved or suspended form. A slight warming, approximately to 50 ⁰ C accelerates the process of Y / water separation; it can be unavoidable if the emulsion is highly viscous from the start.

In addition to the crude oil emulsions mentioned above, which probably regularly have the W / 0 type and do not contain pure water as an aqueous phase, but a more or less concentrated salt solution, the emulsions that occur as sediment in storage tanks and that are in the washing water-insoluble oils for the removal of impurities contained in them resulting emulsions aowit dlt be broken in the cracking of coal or oil products resulting water-containing tars.

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example

2 kg of a folypropylene glycol with a molecular weight of about 2000 and 1 kg of ciinee polyethylene glycol with a molecular weight of about 1000 are dissolved in 2 kg of xylene and by azeotropic distillation of their content of water and low volatile components freed. Then 1 g each of dibutyltin dilaurate and Methylmorpholine added.

With thorough stirring, a solution of 330 g of hexamethylene diisocyanate in 300 g of xylene is initially allowed to flow in slowly and evenly at room temperature. AnEChliei3end is heated to 100 ⁰ C and the desired set Endkonzi.ntrntion smittelmengen by distillation in vacuo or by adding further Lünun. Lower alcohols reduce the viscosity, which can be desirable in many cases.

With the use of 5-40 ppm active substance, different Crude oil emulsions completely split into their components at temperatures.

dene crude oil emulsions at temperatures of about 50 ⁰ C almost

If the starting polyalkylenes are used in the same way. So polyprop .. lenglykol 2000 or the polyethylene glycol 1000 or a mixture of both, then no cleavage takes place.

BAD ORIQiNAL

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example

A unit of 3 moles of polypropylene glycol 1200 and 3 moles of polyethylene glycol 1000 is melted. The alkali contained in it from production is neutralized by adding the appropriate amount of anhydrous acetic acid. It is then diluted with the same volume of toluene and volatile B components are distilled off azeotropically. Instead of this distillation, disruptive impurities can also be removed by simply heating the melt.

Now 5 moles of toluene diisocyanate are briskly under very good conditions Stir, in the absence of solvent, possibly in the kneader, added and stirred for 10 minutes.

The resulting product is soluble in xylene with a slight cloudiness, insoluble in gasoline.

It practically splits petroleum emulsions from northern Germany completely into their components.

Here, too, are the starting polyalkylene glycols and their mixtures ineffective as a splitter.

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example

150 parts by weight of an adduct of 40 # ethylene oxide with a polypropylene glycol with a molecular weight of 2000 were neutralized with acetic acid and freed from volatile components at 120 ° under a vacuum of 25 mm. After approximately the same amount of anhydrous xylenes had been added, a solution of 7 parts by weight of tolylene diisocyanate in the same volume of anhydrous xylene was slowly and evenly added. The viscosity of the approach increases. It still holds 15 minutes at 100 to 120 ⁰ C and then diluted jnit as much methanol that a 40> strength solution.

The presentation process can easily be made continuous if the required amount of diisooyanate is evenly introduced into the stream of polyalkylene glycol.

The preparation produced in this way, added in an amount of 20 ppm, causes the waoser from an Upper Bavarian raw oil to separate quickly and almost quantitatively after passing through the apparatus generally used in the earth oil industry. The initial polyalkylene glycol, on the other hand, releases only about 65 ß> of the existing V / aasers under comparable conditions.

When the splitter is to be used instead of xylene Lb'sung in an aqueous medium, it is appropriate emulsifying additives to be used "for this purpose are all praktiaoh bukannten emulsifiers question _o Good results of Zuaatz of about 5o Gewiohto percent of ammonium oleylmedialansaurem"

BATH ORIGINAL

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example

a) One sets by introducing about 11 mol Äthylenoyyd in

6 moles of tetrahydrofuran in the presence of 2 -Oo antimony pentachloride (calculated on tetrahydrofuran) produce a polyadduct in a known manner.

b) 90 parts of this product are heated to sieve with 1 C) O parts of xylene, with a corresponding separator Care is taken that there are / 3 small amounts of volatile substances removed from the product. 15 parts of hexaraethylene diisocyanate are then added at 120.degree Hour at the same temperature.

To test for splitting effect, a) and b) are in the form of a 0.2 ^ Xf.en solution in xylene in quantities of 10-40 ppm active substance 2 crude petroleum added and at 50 C in an apparatus in which the ge ical is gently moved by rising and falling sheets, held for several hours

a) delivered 53 or 61> * of the available salt water. :; ers in free form, while b) earned almost $ 100> in the same time.

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■ - For β ρ ie 1— 5 -

175 g of a heteric polymer of ethylene oxide and propylene oxide in a molar ratio of 1.0 J 1.25 with a molecular weight of 3500 (calculated from the OH number) are mixed with 0.5 g of glacial acetic acid and at _:. 100-150 ⁰ C freed from volatile components in a vacuum. It is diluted with 130 com xylene and mixed at about 10O ⁰ C and a solution of 8.5 g Tolu; ylendiisocyanat in 50 cc of xylene. After stirring for 1/2 hour, a further 30 ecm of methanol is added.

Used in amounts of 20 to 40 g / t emulsion, this product splits a crude oil from the Upper Bavarian region in a more satisfactory manner Way.

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Claims (4)

-Z ₉ . Claims Process for separating aqueous emulsions of organic liquids, characterized in that the stationary or flowing emulsion of mineral oil consisting of small amounts of polyadducts a) Mixtures of water-soluble and water-insoluble polyalkylene glycols or b) the addition products of ethylene oxide to water-insoluble ones Polyalkylene glycols or o) Products obtained by the simultaneous addition of monomeric Äthjlenoxyd and higher monomeric alkylene oxides from water or glycols with di-isocyanates can be added. 2. The method according to claim 1), characterized in that the polyadducts dissolved in solvents or homogeneously suspended will. 3.) Method according to claim 1 and 2, characterized in that the process of water separation is accelerated by gentle heating. 4. The method according to claim 1, 2 and 3, characterized in that the addition of the polyadducts in coordination with known measures that facilitate the breaking of emulsions, such as additional movement or the application of electrical voltage fields. 909824/1245