DD298805A5 - MISCHDEMULGATOR - Google Patents

Abstract

The invention relates to a Mischdemulgator based on oligomeric polyether alcohols for the cleavage of petroleum emulsions, which is effective at temperatures below 60C and causes a high initial crevice rate. The mixed emulsifier consists of a formulation of 10 to 90 parts by weight of optionally nitrogen-containing polyalkylene oxides with oligomeric aminotriazine of structure I and 90 to 10 parts by weight of optionally nitrogen-containing oligoesters on polyalkylene oxides and dicarboxylic acids of structure IIStruktur IS (E) nAwobei {Mischdemulgator; Erdoelemulsionsspaltung; Demulgatormischung; Polyether alcohol, oligomer; Demulsification temperature; Emulsion splitting speed; demulsifier; Aminotriazine residue, oligomer; diethylenetriamine}

Description

Field of application of the invention

The invention relates to mixed emulsifiers for the separation of petroleum emulsions.

Characteristic of the known state of the art

In the extraction of oil from underground deposits petroleum emulsions are promoted to a considerable extent. By natural emulsifiers contained in petroleum, e.g. Naphthenates and other surfactant compounds stabilize these emulsions. Metal sulfides and clays or other finely divided mineral constituents present in petroleum also stabilize these emulsions.

For a technical processing of the petroleum, the splitting of these primary promoted emulsions is necessary. In slitting plants, the emulsions are split in the temperature range from 2O-85 ° C with the addition of 10-300 ppm of surfactants, demulsifiers. The separated largely salt and water-free crude oil is then supplied as so-called commercial petroleum for processing in the refineries.

It is in the nature of the matter that the stabilization of the petroleum emulsions takes place in the most varied ways according to the geological conditions of the petroleum deposit and the chemical composition of the petroleum. Accordingly, various demulsifiers are necessary for working up the petroleum because a special demulsifier does not effectively crack any petroleum emulsion.

In particular, the nonionic surfactants have been proven for this purpose.

Oxyethylene-oxypropylene block copolymers, mixtures of water-soluble and -insoluble polyalkylene glycols which have been reacted with aliphatic or aromatic diisocyanates, are known from DE-PS 1127 082 and DE-PS 1495827. U.S. Patent Nos. 3,206,214 and 3,202,615 refer to common reaction products of oxyethylene-oxypropylene block copolymers or alkylphenol resin oxalkylates with dicarboxylic acids or their anhydrides, such as diglycolic acid and maleic anhydride. Oxalkyiates of N, N "-Tra- (5-oxypropylpropylol) -N '- {2-oxypropyl) -diethylöntriamins are described in DD-PS 151175. In DD-PS 229136 a method for dewatering and desalination of petroleum under The use of oligomers of alpha-methylstyrenediol or its polyglycol ethers is described Diurethanes of the general formula

R ₂ -C ₆ H - 'C ₃ H _e O) .- (C ₂ H ₄ O) ₁₎ -CÜNH-R, -NHCO- (OC ₂ H ₄ ) ₁ - (OC 3 H 6), - OC ₆ H ₄ -R ₂ where

R ₁ : aromatic, aliphatic or cycloaliphatic radical having at least 6 C atoms

a: 10 to 40 oxypropylene units

b: 5 to 45 oxyethylene units

b / a: 0.3 to 1.9

R ₂ : 4 to 12 C atoms

are described in DD-PS 231948 as effective demulsifiers below 30 ⁰ C. DE-PS 2434545 mentions mixtures of alkoxylated phenolic resins, glycol esters, polyol, polyalkylene glycols, alkyl / arylsulfonates, alkoxylated amines or short-acting dicarboxylic acids and high molecular weight polyols with alkyl ether sulfates as emulsion breakers. Polyimines of various structures are used as demulsifiers z. For example, in DE-PS 3404 538, DE-PS 2227 546 and DE-PS 2719978. According to DE-PS 3404538 a polyimine of the structure

X = ^ - CH ₂ -CH ₂ -NH-Ic-H

a and b are independently 0 to 600, a + b = 50 to

c = 0 to is with an alkylating agent of the structure

A-Z-A

Z = direct bond or-C _n H _2n -A = -CH ₂ -YY = CI, Br, J, OH, sulphonyloxy radical

is reacted and used the reaction product for the separation of oil waste water steam-flooded oil deposits. In a large number of patents, alkoxylated formaldehyde resins, their mixtures or their subsequent reaction products with diisocyanates are described as effective domulgators (DE-PS 2445873, DE-PS 3223629, DE-PS 3223691, DE-PS 1642825). The demulsifiers according to the prior art adhere to the disadvantages that they either insufficiently split at temperatures below 60 ° C, they can be produced only after elaborate syntheses or the economy of their production is reduced by low space / time yields.

Object of the invention

The aim of the invention is to provide novel compounding emulsifiers for the separation of petroleum emulsions, which do not have the disadvantages of the demulsifiers according to the prior art.

Explaining the nature of the invention

The invention has for its object to develop Mischdervulgatoren based on oligomeric Polyetheralkoholen to have at temperatures below 60 ° C petroleum emulsions and a high initial nip speed clalton. According to the invention the object is achieved in that as a mixed demulsifier, a formulation of 10 to 90 parts by weight of compounds of structure I.

S- (E) _n -A

E = - (- C ₂ H ₄ -CH ₁ -n = O or 1 A = - (- C ₃ H ₃ -O-Iy- (C ₂ H ₄ -CH _x -TT = randomly distributed mixture of an oligomeric aminotriazine residue and -H , wherein on average per molecule at least one

oligomeric aminotriazine radical is S = X, Y, Z is X = HO-, where inln = 1, x = 5 to 40 and yy = 32 to 65,

AO- (CH ₂ ) _m

^Y ~ ^ T N- (CH ₂ ), Jp ₅ where in I n = O, m = 2 or 3,

AO- (CH ₂ ) O ₁ """" ^ ^ x = 5 to 30, y = 15 to 50,

A A

2 .- = J 1 N-CH ₂ -CH ₂ -N-CH ₂ -CH ₂ -NCT,

A wherein in I η = 0, χ = 6 to 20, y = 3 to 25 and 90 to 10 parts by weight of compounds of the structure II

R ₁ -QR ₂

where Q = X, Y, Z

X = -O- (C ₂ H ₄ O-) _x - (C ₃ H ₆ O-) _r (C ₂ H ₄ O-) _x -

R ₁ = - (- CO-R-CO-Q-) ₂ -H

R = -CH = CH-, phenylene radical

χ = O to 50

y = 18 to 130

ζ = the statistical average is 2

C ₂ H ₄ O-

γ = NC ₂ H ₄ OR ₂

C ₂ H ₄ O-

R, = - _{e C3H O-) _y - {CjH4a-) x - (- CO-R-COO- (C ₂ H40-) _x - (C ₃ H _e O) _v -0-) -HR _{1 2} = - (C ₃ H _e O-) _y - (C ₂ H ₄ C> -) _x -H χ = 5 to 30

y = 15 to 50

ζ = on a statistical average 2

R = -CH = CH-, phenylene radical is r

/ ²

Z = N-CH ₂ CH ₂ -IM-CH ₂ CH ₂ -N

^R 2

Ri = - (C 3 H ₆ O) _y - (C ₂ H ₄ O-) _x - (- CO-R-C00- (C 2 H '0-) _x - (C ₃ H ₆ O-) _y -Q-) ₁ -HR ₂ = - (C ₃ H ₆ OV (C ₂ H ₄ O -) ,, ^ χ = 6 to 20

y = 3 to 25

ζ = on a statistical average 2

R = -CH = CH-, phenylene radical,

optionally used in solution.

Mixtures of this composition are effective demulsifiers, which cause the destruction of the crude oil emulsions even at split temperatures of 20 ° C. It is a particular advantage of these demulsifiers that they split the crude oil emulsions after a short reaction time. It is also advantageous that the more oleophilic products do not favor the solubilization of petroleum in the salt water separated from the emulsion and thus an environmentally friendly technology is easier to implement.

embodiments

The demulsifying power of the described demulsifiers according to the invention was tested on artificial remulsions of chemically untreated crude oil and salt water. The salt water content of the remulsions can be found in the examples listed. The demulsifiers were used as 1% solutions in xylene / isopropanol (3: 1) or as 50% solutions. The practical implementation was analogous to the bottle test

 The following demulsifiers were tested:

No. Composition of compounds of structure Wl

1 20 I χ = 15, V = 34, η = 1, S = X 2 70 χ = 25, y = 58, η = 1, S = X 3 50 χ = 5, y = 32. η = 1, S = X 4 85 χ = 9, y = 28, n = 0, S = Y m = 2 5 30 χ = 20, y = 20, n = 0, S = Y m = 3 6 50 χ = 28, y = 42, n = 0, S = Y (T) = 2 7 40 X = 10, y = io, n = 0, S = Z 8th 30 χ = 6, Y = 5, n = 0. S = Z 9 70 χ = 18, V = 22, n = 0. S = DE

% Il y = 10 80 χ = 10, Q = Z y = 34 30 χ = 15, R = phenylene radical Q = X, y = 42 50 χ = 28, Q = Y y = 48 15 χ = 36, R = -CH = CH- Q = X, y = 10 70 X = 16, Q = Z y = 20 50 χ = 20, Q = Y y = 28 60 χ = 9, Q = Y y = 40 70 X = 19, Q = Y y = 5 30 χ = 6, Q = Z

To better explain the or demungsgemgäßen demulsifiers some Polyetheralkohole type III

N XC_C ₂ H ₄ -OR ₂

R1.R2.R3 - - (- C ₃ H _e O-) _y - {- C _J H ₄ O-) _x -H χ = 5 to 30 y = 15 to 50

and type IV

N-CH ₂ CH ₂ -N-CH ₂ CH ₂ -N

R ₄

R ₂ ^R 5

R until R ₆ = - (- C ₃ H ₆ O-) _x - (- C ₂ H "O-) _y -H x = 6 to 20 y = 3 to 25

and which are an initial component of the demulsifiers, are also included in the tests:

Type 7 χ = 28, y = 42

III 8 χ = 9, y = 28 9 χ = 10, y = 40

IV 10 χ = 10, y = 10

Investigations carried out:

Split Test A

Petroleum no. 4,35VoI .-% salt water content, demulsifier concentration 35ppm, cracking temperature 20 ⁰ C

Product No .: Split result in% 0.5 h 1h 10min 69 92 1 35 58 88 2 45 47 81 3 30 52 88 4 38 43 79 5 24 61 95 6 41 1 5 7 0 1 8th 8th 0 1 7 9 0

Split Test B

Petroleum no. 5.30% by volume salt water content, demulsifier concentration 90 ppm, cracking temperature 20 ° C., metered in product form

Product No .: Split result in% 1h 2h 0.5 h 41 64 1 20 48 71 2 26 45 73 3 21 52 85 4 33 33 52 5 10 67 78 6 41 1 2 7 0 0 1 8th 0 1 1 9 0

Claims (2)

1. Mischdarnulgator for the separation of petroleum emulsions, characterized in that a formulation of 10 to 90 parts by weight of compounds of structure I. S- (E) _n -A E = - (- C ₂ H ₄ -CH _x n = O or 1 A = - (- C ₃ H ₆ -O-) _y - (C ₂ H ₄ -O-) _x -TT = randomly distributed mixture of an oligomeric aminotriazine residue and H, being on average there is at least one oligomeric aminotriazine residue per molecule S = X, Y, Z X = HO-, where in I η = 1, x = 5 to 40, and y = 32 to 65, AO- (CH ₂ ) _m AO- (CH ₂ ) "^ x = 5 to 30, y-15 to 50 is-, where in I η = O, χ = 6 to 20, y = 3 to 25 and 90 to 10 parts by weight of compounds of the structure II R ₁ -QR ₂ Q = X, Y, ZX = -O- (C ₂ H ₄ O-) _x - (C ₃ H ₆ O-) _y - (C _{2 H4O-)) <R 1} = - (- CO-R-CO -Q-) _z -HR ₂ = HR = -CH = CH-, phenylene radical χ = O to 50 y = 18 to 130 ζ = on a statistical average 2 ^If C ₇ H ₄ O- Y = NC ₂ H ₄ OR ₂ C ₂ H ₄ O- R ₁ = - (C3H ₆ O) _y - (C ₂ H ₄ O-) _x - (- CO-R-COO- (C 2 H ₄ O-) _x - (C3H ₆ O) _y -Q-) _z -HR ₂ = _ (c ₃ H ₆ O-) _y - (C ₂ H ₄ O-) _x -H χ = 5 to 30 y = 15 to 50 ζ = on a statistical average 2 R is -CH = CH-, phenylene radical Rd N-CH ₂ CH ₂ -N-CH ₂ CH ₂ -N R ₂ Ri = - (C ₃ H ₆ O-) _y - (C ₂ H ₄ O-) _{) (} - (- CO-R-COO- (C ₂ H ₄ O-) _x - (C ₃ H ₆ O-) _v -Q-) _z -HR ₂ = - (C ₃ H _e O-) y- (C ₂ H ₄ O-) _J rH χ = 6 to 20 y = 3 to 25 ζ = on a statistical average 2 R = -CH = CH-, phenylene radical
is, is used. 2. Mischdernulgator according to claim 1, characterized in that 25 to 75 parts by weight of compounds of the structures I and 25 to 75 parts by weight of compounds of the structures II are used.