DD298809A5 - NON-SPECTRUM DEMULATOR MIXTURE - Google Patents

Abstract

The invention relates to a nonionic demulsifier mixture for the separation of petroleum emulsions, which is effective at temperatures below 60 ° C and allows a high initial crevice rate. The mixture consists of 10 to 90 parts by weight of a Triethanolaminpolyalkylenoxids with oligomeric Aminotriazinrest of structure I and 90 to 10 parts by weight of a Diethylentriaminpolyakylenoxids with oligomeric Aminotriazinrest the structure II {demulsifier mixture; Erdoelemulsionsspaltung; Demulsification; Low temperature emulsion breaking; Emulsion splitting speed; Demulsifier, nonionic; Aminotriazine residue, oligomeric; Triethanolaminpolyalkylenoxid}

Description

and 90 to 10 parts by weight of compounds of structure II

R ₁ R ₁

R ₁ = - (- C ₃ H ₆ O-) _x - (- C ₂ H ₄ O-) _y -R ₂

χ = 6 to 20

y = 3 to 25

R ₂ = randomly distributed mixture of an oligomeric Aminctriazinrestes and -H, wherein

an average of at least one oligomeric aminotriazine residue per molecule

represent.

2. Nonionic demulsifier mixture according to claim 1, characterized in that 25 to 75 parts by weight of compounds of structure I and 25 to 75 parts by weight of compounds of structure II are used.

Field of application of the invention

The invention relates to a nonionic demulsifier mixture for the separation of petroleum emulsions. ^s

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, such as. As naphthenates and other surface-active compounds, these emulsions are stabilized. 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 cracking plants, the emulsions in Temperaturbe / calibration of 20-85 ⁰ C with the addition of 10-300 ppm of surfactants, demulsifiers are cleaved. 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 1127082 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 Harzoxalkylate with dicarboxylic acids or their anhydrides, such as diglycolic acid and maleic anhydride. Oxalkylates of N, N "-tetra- (5-oxypropylpropyl) -N '- (2-oxypropyl) -diethylenetriamine are described in DD-PS 151175. DD-PS 229136 discloses a process for dewatering and desalting petroleum Use of oligomers of the alpha-Methylstyro'diols or its polyglycol ether described Diurethano the general formula

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

mean,

are described in DD-PS 231948 as effective demulsifiers below 3O ⁰ C. German Patent 2434545 mentions mixtures of oxalkylated phenolic resins, glycol esters, polyols, polyalkylene glycols, alkyl / arylsulfonates, alkoxylated amines or short-chain dicarboxylic acids and high molecular weight polyols with alkyl ether sulfates as emulsion breakers. Polyimines of various structures are used as demulsifiers z. B. in DE-PS 3404 538, DE-PS 2 227 546 and DE-PS 2 719 978 called. According to DE-PS 3404! 538 a polyimine of the structure

X = - (- CH ₂ -C

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

with an Aikylierungsmittel the structure

A-Z-A

Z = direct bond or-C _n H _2n -

Y = Cl, Br, J, OH, sulphonyloxy radical

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 demulsifiers (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 6O ⁰ C, they can be produced only after elaborate syntheses or the economy of their production is reduced by low space / time yields.

Aim of the invention

The aim of the invention is to provide new nonionic demulsifier mixtures 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 nonionic demulsifier mixtures for the cleavage of petroleum emulsions based on oligomeric polyether alcohols, which split at temperatures below 6O ⁰ C petroleum emulsions and have a high initial crevice rate.

According to the invention the object is achieved in that it is a mixture of 10 to 90 parts by weight of compounds of structure I.

C ₂ H ₄ -OR ₁ N -C ₂ H ₄ -OR ₂ C / nH Λ Ο "" RT

R ₁ , R ₂ , R ₃ = - (- C ₃ H ₆ OVIC ₂ H ₄ OI _x -R ₁

χ = 5 to 30

y = 15 to 50

R ₄ = randomly distributed mixture of an oligomeric Aminotriazinrestes and -H, wherein on average per molecule

at least one oligomeric aminotriazine residue is present and 90 to 10 parts by weight of compounds of structure II

¹ "" ~ - ~ - N-CH ₂ CH ₂ -N-CH ₂ CH ₂ -NC ^ TR ₁ - ^ "" * IR ₁

^R l

R ₁ = - (- C ₃ H _e O-) _x - (- C ₂ H ₄ O-) _r R ₂ χ = 6 to 20 y = 3 to 25

R; = randomly distributed mixture of an oligomeric Aminotriazinrestes and -H, wherein on average per molecule at least one oligomeric Aminotriazinrest exists

optionally in solution.

Particularly effective nonionic demulsifier mixtures are those in which 25 to 75 parts by weight of compounds of structure I and 25 to 75 parts by weight of compounds of structure II are used.

Products 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 olfophilic products do not favor the solubilization of petroleum in salt water separated from the emulsion, and thus e'.ne environmentally friendly technology is easier to realize.

Highly fissionable petroleum emulsions, which are hardly fissile with demulsifiers according to StJind technology, can be worked up with the new demulsifiers.

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 xylene / isopropanol (3: 1) or as 50% solutions. The practical implementation was analogous to the bottle test

 The following demulsifiers were tested:

nc composition = 7, y = 36 80% II, x = 10, y = 10 1 20% I, χ = 28, y = 42 15% II, x = 6, y = 5 2 85% I, χ = 9, y = 28 30% II, x = 18, y = 22 3 70% I, χ = 19, y = 40 60% II, x = 12, y = 16 4 40% I, χ = 7, y = 36 50% II, χ = 14, y = 12 5 50% I, χ = 7.y = 36 50% II, X = 6, y = 5 6 50% I, χ

To better explain the demulsifiers according to the invention were ninige products according to the prior art with the general formula III

C ₂ H ₄ -OR ₁ N <- C ₂ H ₄ -OR ₂ -C ₂ H ₄ -OR ₃

Ri, R ₂ , R ₃ = - (- C ₃ H ₀ O - ^ - IC ₂ H ₄ OI _x -H χ = 5 to 30

y = 15 to 50

and the general formula IV

^ T N -CH ₂ CH ₂ -N-CH ₂ CH ₂ -N

Ri = - (- C ₃ H _e O-) _x - (- C ₂ H ₄ O-) _/ -H χ = 6 to 20 y = 3 to 25

and which are a starting component of the demuigators, are also included in the tests:

7 bO% III, χ = 7, y = 36 50% IV, χ = 10, y = 10 8th 85% III, x = 28, y = 42 15% IV, X = 18, y = 22 9 20% III, x = 7, y = 36 80% IV, χ = β, Υ = 5

Investigations carried out:

Split Test A

Oil No. 10a, 3CVoI ·% salt water content, demulsifier concentration 70 ppm, cracking temperature 20 ° C, dosed in the form of goods

Split result in% 0.5 h 2h Product No .: 10min 53 75 1 38 49 81 2 25 56 90 3 42 33 68 4 19 48 72 5 35 55 82 δ 36 0 1 7 0 0 2 8th 0 0 1 9 0

Split Test B

Petroleum No.6,45Vol .-% saltwater content, demulsifier concentration 50ppm, spa temperature 2O ⁰ C, dosed in product form

Split result in % 2h Product No .: 10min 1h 87 1 28 47 90 2 26 54 93 3 33 61 75 4 16 44 80 5 19 38 86 6 29 43 10 7 0 5 7 8th 0 3 9 9 0 4

Claims (1)

1. Nonionic Demulgatorrrrschung for the separation of petroleum emulsions, characterized in that it comprises a mixture of 10 to 90 parts by weight of compounds of structure I. ^ C ₂ H ₄ -OR ₁ N <- C ₂ H ₄ -OR ₂ ^ C ₂ H ₄ -OR ₃ Rl »F? 2i R3 ⁼ - (- y χ = 5 to 30 y = 15 to 50 R ₄ = statistically distributed oligomeric aminotriazine residue or H, wherein on average pro Molecule is at least one oligomeric aminotriazine residue