NO162913B - APPLICATION OF ORGANOSILICIUM-MODIFIED POLYDIANS AS DEMULGATORS FOR OIL OIL / WATER EMULSIONS. - Google Patents

Abstract

Use of organosilicon modified polydienes of the general formula. wherein Z represents chain limiting groups,. R1 in the molecule is the same or different and means hydrogen or methyl residue ,. R 2 in the molecule is the same or different and represents an optionally fluorinated alkyl or alkylaryl radical having 6 to 24 carbon atoms. R 2 in the molecule is the same or different and represents the residue (R 40 -) m Y, where R 4 represents alkylene radicals having 2 to 4 carbon atoms, m = 2 and Y represents an alkyl radical having 1 to carbon atoms, and. as average. w 0 ,. x = 0 ,. y i ,. a = 0 to 2,. b = 0 or 1. 0 <c <3, where 0 <a + c <3 ,. as dismulgators for petroleum / water emulsions.

Description

The present invention relates to the use of organosilicon-modified polydienes as demulsifiers for petroleum/water emulsions.

During transport, a large part of the crude oil contains smaller or larger amounts of salt water in emulsified form. Such emulsions which predominantly act as water/oil emulsions must be divided into their phases, as the salt water contained in the emulsion would interfere with further processing of the crude oil, especially during transport and during distillation.

The separation of such petroleum emulsions is successful either by deposition, heat treatment, centrifugation, by the application of electric fields or by the addition of demulsifiers, respectively the combination of several methods.

The transported crude oil emulsions are mostly too stable to be broken alone or by sedimentation, filtration, centrifugation or heating. In contrast, demulsifiers already cause a separation of the emulsion in small concentrations.

Demulsifiers have already been proposed in large numbers. This is mainly because the different petroleum oils have different compositions, and demulsifiers that are suitable for breaking emulsions and petroleum oils from one place of origin are unsuitable for petroleum emulsions from other deposits. The known dispersants therefore act more or less distinctly specifically on the individual petroleum oils.

Alkyl sulfates and alkyl aryl sulfonates as well as petroleum sulfonates in the form of amine salts have already been proposed as demulsifiers. Furthermore, addition products of ethylene oxide to suitable compounds with an active hydrogen atom such as e.g. alkylphenols, castor oil, fatty acid, fatty alcohol, alkylphenol and aldehyde resins. Corresponding information can be found, e.g. in the book "Oberflachenaktive Anlagerungsprodukte des Ethylenoxids" by N. Schonfeld, Wissenschaftiiche Verlagsgesellschaft mbH. , Stuttgart, 1959, page 295.

In DE-PS 10 37 130 it is mentioned that certain known polyoxyalkylene-polysloxane block mixture polymers have outstanding properties as demulsifiers for petroleum emulsions of the water/oil type of different origins<1> and also act as demulsifiers in very small quantities, i.e. smaller quantities than the products in according to the state of the art. The polyoxyalkylene-polysiloxane block blend polymers have polyoxyalkylene blocks of a molecular weight of 500 to 4000, consisting of polyoxyethylene, polyoxypropylene blocks in weight ratios of 40:60 to 100:0. The polysiloxane blocks have 5 to 50 silicon atoms per block.

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Subject matter of DE-PS 22 50 920 are mixtures of 0.2 to 30% by weight of the above-mentioned polyoxyalkylene-polysiloxane block blend polymers with 70 to 99^8% by weight of silicon-free demulsifiers, which consist of alkylene oxide addition products to organic compounds containing reactive

-Ia-

reaction products of alkylene oxides with alkylphenolaldehyde resins, block and mixed polymers of propylene oxide and ethylene oxide, their reaction products with dicarboxylic acids or diisocyanates as well as mixtures of these products. Thereby it was determined that the mixtures according to German patent

22 50 920 has particularly favorable properties with regard to demulsification and at the same time preventing foaming. in

From DE-PS 23 21 557 silicon-containing block copolymers based on organosilicon-modified polydienes are known. These compounds are obtained; by adding silanes containing hydrogen residues to polydienes, as the silanes also have halogen, alkoxy or acryloxy acid residues which are then reacted with the polyethers. <:> These compounds are versatile. They are additives in the production of polyurethane foam, they are suitable as a propellant, they can be used as a preparation agent in the textile industry or used in cosmetics. As a further purpose of use, the use of the compounds as demulsifiers for the separation of petroleum/water emulsions has been mentioned.

The present invention is based on the task of providing compounds which are particularly suitable as demulsifiers, especially for separating petroleum/water emulsions, as they separate the water contained in the petroleum as quickly and completely as possible. In addition, efforts must be made to ensure that the compounds retain their demulsifying properties against the various types of crude oils and are therefore as universally applicable as possible. The demulsifiers must also be compatible and miscible with those from the state of the art in order also in this way, if possible, to expand their area of application.

Certain organosilicon modified polydienes have been found to meet these requirements. Special characteristics of these compounds are Si-O-C attached long-chain alkyl or alkylphenyl groups, which obviously contribute to an increased interaction with the oil phase in the petroleum emulsions.

The invention therefore relates to the use of organosilicon-modified polydienes with the general formula

where X means chain-limiting groups,

R<1> in the molecule are the same or different and mean a hydrogen atom or a methyl residue,

R<2> in the molecule are the same or different and mean an optionally fluorinated alkyl or alkylphenyl residue with 6 to 24 carbon atoms,

r<3> in the molecule are the same or different and mean the residue (R<4>0-)mY, with R<4> comprising alkylene residues with 2 to 4 carbon atoms, m 2 2 and Y is an alkyl residue with 1 to 4 carbon atoms, and

being average

w 2 0

x 2 0

y 3

a = 0 to 2

b = 0 or 1

0 < c < 3, since 0 < a + c < 3,

as demulsifiers for soil oil/water emulsions.

1 the formula means Z chain-limiting groups which are provided in advance by the chosen production process for poly-i

the diet. Examples of such groups are -H, CH2=CH-CH2-CH2-, -CH2-CH2-OH, -COOH, -CH3, -C4H9, -C6H5, -CH2-C6H5, -Si(CH3)3.

R<1> in the polymeric molecule can be the same or different and mean hydrogen or the methyl residue.

1

R<2> can likewise be the same or different in the polymeric molecule. Thereby, R<2> is an alkyl or alkylphenyl residue with 6 to 24 carbon atoms, preferably 18 to 24 carbon atoms, especially 12 to 24 carbon atoms, the alkyl group having to be branched. Branched alkyl groups with a higher carbon content have the advantage that the viscosity of the modifier is reduced. The alkyl radicals can also be fluorinated, especially partially fluorinated. Examples of such fluorinated residues are

CF3-(CF2-)6CH2-, CF3(CF2-)5CH2-CH2-, jCF3-(CF2-)7-CH2-CH2-.

1

R^ in the polymeric molecule can be the same or different and mean the polyether residue with the formula (R<4>0-)mY. R<4> is an alkylene group with 2, 3 or 4 carbon atoms. Also R<4> in the middle molecule can be the same or different. Polyethers with polyethylene oxide and/or polypropylene oxide units are preferred, since in the case of mixed polymers these units can appear statistically mixed or appear separately in blocks. Products with a secondary OH group are preferred. The oxyalkylene block can thus be composed of oxyethylene and propylene and/or oxybutylene units. Preferably, the oxyalkylene residue consists of at least 40% by weight of oxyethylene units. m > 2. Preferably, m has such a value that the molecular weight of the residue R<3> amounts to 300 to 600. Y is an alkyl residue with 1 to 4 carbon atoms. Particularly preferred are the methyl and butyl residues.

Long numbers for the indices w, x, y, a, b and c refer to the average molecule. This means that within the polymer block formation they can assume different values. They must, however, on average meet the specified conditions.

Compounds are preferably used in which the units containing unsubstituted double bonds and denoted by the indices w and x are present in an amount of from 25 to 80 mol% of the sum of the units w + x + 7.

Compounds in which the index b is on average 1 and where R<2> is derived from a primary alcohol or phenol are particularly preferred.

Compounds which, for example, are used according to the invention are:

C:0 ratio of the residue R<4> = 2.2:1. ! l

C:0 ratio of the residue R<4> = 2.5:1.

t

C:0 ratio of the residue R<4> = 2.2:1.

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i

C:0 ratio of the residue R<4*> - 2.2:1

C:0 ratio of the residue R<4**> - 2.5:1

The compounds of formula I that can be used according to the invention can be prepared in a manner known per se, which is not covered by the invention, by at least y mol of silanes of the general formula

where X means a halogen, alkoxy or acyloxy acid residue, is added in a manner known per se to polydienes of the general formula having a molecular weight of from 300 to 200,000 in the presence of noble metal catalysts, and the formed addition products include at least y(3-a-c) moles of compounds with the general formula

IN

IN

°g y-c m°l compounds with the general formula

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The residues R<1>, R<2>, R<3> and Z as the indices a, b, c, w, x and y have the meaning already indicated.

The implementation of such a method is analogous to that described in German patent 23 21 557.' As catalysts for adding the silanes of formula VI to the polydienes of formula VII, platinum catalysts are used in particular, such as e.g. hexachloroplatinic acid or platinum ethylene pyridine dichloride. The reaction is conveniently carried out in the presence of a solvent, especially toluene. The deposition of the silane to the polydiene preferably takes place at elevated temperatures, e.g. at the boiling point of toluene.

The conversions of the intermediates formed with the compounds of formula

and with compounds of formula 1 i

suitably also takes place in the presence of a solvent, with toluene again being preferred. However, other inert solvents such as e.g. methylene chloride, glycol ether or cyclic ethers. Have X

the importance of a halogen residue, the liberated halogen hydrogen is suitably captured with ammonia. Instead of ammonia, amine can also be used. Similarly, when X has the meaning of an acyloxy acid residue, the liberated carboxylic acid can be neutralized. If X is the meaning of an carboxylic acid residue, then it pays to remove the liberated low molecular weight alkanol from the reaction mixture by distillation. For this reason, it is also preferred to use the methoxy or ethoxy residue as the carboxylic acid residue.

The demulsifiers according to the invention are added to the petroleum/water emulsions, preferably in quantities of 1-300 ppm. It is also possible to dissolve the demulsifiers in a solvent such as e.g. toluene and adding the solution to the petroleum. The compounds lead to a rapid and very complete separation of water from the crude oil. The compounds do not interfere with the further processing of the oil and in particular do not lead to foaming problems during distillation and processing of the oil.

In the following examples, the production of the demulsifiers that can be used according to the invention and their technical application properties are shown.

General first in11ing procedure

An approx. A 50% toluene solution of the polydiene is prepared with 15 mg of platinum ethylene pyridine dichloride per mol SiH as a catalyst at the boiling point of toluene, and the desired amount of hydrogen silane is added dropwise to the solution. After completion of the reaction, the acid value of the product is determined and the corresponding amount of alcohol polyether mixture with a molar amount of triethylamine is added. After filtering and distilling off the toluene, you get the desired end product, which can also possibly be stabilized by additions.

Demulsification test

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Two different North German crude oils were used, oil A with 48% water and oil B with 28% water. To each 50 ml of crude oil in a calibrated observation glass, 20 ppm of the various substances were added and the secreted amounts of water in ml were determined after specific times. ; The temperature was kept constant at 50* C during the experiment. Polyethers with different E0/P0 ratios and their reaction products with polydiene-water-hydrogen-silane adducts and products according to the invention which additionally contained long-chain alcohol derivatives were investigated.

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For comparison with the state of the art, example 1 in the German patent 16 42 825 and 23 21557 was revised.

In the following table, which reproduces the test results, the following substances are designated by numbers from 1 to 13.

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1) Polyether C4Hg0(CnH2n0)36>gH

n=2and3, C:0=2,2:1

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2) Polyether C4HgO(CnH2n0)33f8<H>

n = 2, 3 and 4, C:O = 2.5:1

3)

4)

6) Formula I with w = 5,x = 25,y = 30, R<1> = H,

R<2> = iso-octadecyl-, a-l, b-l, C-o

7) as 6, with a=l,c = 2, R<3> = C4Hg(0Cn<H>2n)36.9» n ■= 2 and 3, C:0 = 2.2:1 8) as 7, with R<3> - C4H9(0CnH2ri )33 ,g >

n = 2, 3 and 4, C:= = 2.5:1

9) as 6, with R<2> = isotridecyl-,

R<3> = C4Hg( (0CnH2n)33^).

a = l,b = l, c = l,

n = 2 and 3, C:0 2.5:1 10) as 9, with R<2> = Isoctadecyl-, = C4H9(0CnH2n)36>q,

n = 2 and 3, C:= = 2.2:1

11) as 10, with R<2> nonylphenyl-

12) Product from DE-PS 16 42 825, example 1

13) Product from DE-PS 23 21 557, example 1

When comparing examples 9 to 12 according to the invention with the examples which do not fall within the scope of the invention, it appears that only in the presence of polyethers and long-chain alcohols in the molecules of formula I can a very good effect be achieved in the demulsification of petroleum/water emulsions.

The comparison with prior art demulsifiers (Examples 12 and 13) demonstrates the superiority of the compounds of the invention.

Claims (1)

Use of organosilicon-modified polydienes with the general formula in which Z means chain-limiting groups, R<1> in the molecule are the same or different and mean a hydrogen or methyl residue, R<2> in the molecule are the same or different and mean an optionally fluorinated alkyl or alky <i>lphenyl residue with 6 to 24 carbon atoms, R<3> in the molecule are the same or different and means the residue (R<4>0-)mY, where R<4> means alkylene residues with 2 to 4 carbon atoms, 1 m 2 2 and Y means an alkyl residue with 1 to 4 carbon atoms, and where on average w > 0, x > 0, y 3, i a = 0 to 2, b = 0 or 1 0 < c < 3, where 0 < a + c < 3 , as demulsifiers for soil oil/water emulsions.