DD298812A5 - demulsifier - Google Patents

Abstract

The invention relates to a demulsifier for the separation of Erdoelemulsionen, which is effective at temperatures below 60C and has a high initial crevice rate. The demulsifier consists of a mixture of 85 to 99.5 parts by weight of alkylene oxide block copolymers having an oligomeric aminotriazine moiety of structure I and 15 to 0.5 parts by weight of an oligomeric aminotriazine residue-containing polyethylene oxide of structure II. {Demulsifier; Erdoelspaltung; Demulsification; Emulsion splitting speed; Ethylene oxide-propylene oxide adduct; aminotriazine}

Description

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

a: 10 to 40 oxypropylene units

b: 6 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 30 ° C. German Patent 2,434,545 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. ^R 'olyimine different structure are called as demulsifiers, for example in DE-PS 3404538, DE-PS 2227546 and DE-PS 2719978.

According to DE-PS 3404538 a polyimine of the structure

X = - (- CH ₂ -CHj-NH-VH a and b independently 0 to 600, a + b = 50 to

with an alkylating agent of the structure

A-Z-A

Z = direct bond or -C _n H _2n -A = -CH ₂ -Y

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

implemented 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 60 ⁰ 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 demulsifiers 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 demulsifiers 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 creep speed.

According to the invention the object is achieved in that the demulsifier of a mixture of 85 to 99.5 parts by weight of compounds of structure I.

R ₁ -O - (- CjH ₄ O-) _x - (- C ₃ H eO-) _y - (- C ₂ H ₄ O-) _K -R ₁ where

χ = 5 to 40 y = 32 to 65

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

and 15.0 to 0.5 parts by weight of compounds of structure II

Rr-OIC ₂ H ₄ CH ₁ -R ₂ where

ζ = 10 to 50 and

R ₂ = randomly distributed mixture of an oligomeric Aminotriazinrestes and -H, wherein on average per molecule at least one oligomeric aminotriazine residue is present

optionally in solution.

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 Roherdölemulsionen after an exposure time of about 10 minutes, while demulsifiers according to the prior art often act after a contact time of at least 30 minutes significantly.

It is advantageous in terms of the lowest possible use concentration of the demulsifiers, if the molecular weight of the oxypropylene unit in the compounds of structure I is 2600 to 3400.

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.

Highly fissionable petroleum emulsions, which are scarcely fissile with demulsifiers according to the prior art, 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 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

1 88% l, x = 15, y = 34 12% ll, z = 30

2 96% l, x = 25, y = 58 4% ll, z = 15

3 93% l, x = 36, y = 48 7% ll, z = 50

4 95% l, x = 20, y = 48 5% ll, z = 10

5 98% l, x = 5, y = 32 ll

To better explain the demulsifiers according to the invention, some polyether alcohols of the type III H-0 - (- C ₂ H "O-) x - (- C ₃ H _e 0-) _y - (- C ₂ H 40 -) _x -H

x = 5 to 40

y = 32 to 65

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

6 x = 15, y = 34

7 x = 20, y = 48

8 x = 5, y> = 32

Investigations carried out:

Split Test A

Oil no. 6,40VoI .-% salt water content, demulsifier concentration 30ppm, cracking temperature 20 ⁰ C

Product No .: Split result in% 0.5 h 1h 10min 72 90 1 55 88 97 2 70 77 94 3 65 90 98 4 72 63 79 5 44 5 25 6 1 38 65 7 5 11 48 8th 1

Split Test B

Petroleum No. 11.25% by volume salt water content, demulsifier concentration 100ppm, cracking temperature 20 ° C

Product No .: Split result in % 1h 10 min 0.5 h 55 1 10 25 72 2 37 56 65 3 21 48 81 4 31 69 40 5 14 21 1 6 0 0 35 7 1 9 6 8th 0 1

Claims (2)

1. demulsifier for the separation of petroleum emulsions, characterized in that it consists of a mixture of 85 to 99.5 parts by weight of compounds of structure I. R, _O - (- C ₂ H4O-) _x - (- C3H ₆ O) _y - (- C2H ₄ O) _x -R ₁
in which χ = 5 to 40
y = 32 to 65 R ₁ = randomly distributed mixture of an oligomeric Aminotriazinrestes and -H, wherein on average per molecule at least one oligomeric Aminotriazinrest exists and 15.0 to 0.5 parts by weight of compounds of structure II R ₂ -OIC ₂ H ₄ O-) _Z -R ₂
in which ζ = 10 to 50 and R ₂ = randomly distributed mixture of an oligomeric Aminotriazinrostes and-H, wherein on average per molecule at least one oligomeric Aminotriazinrest exists is
consists. 2. Demulsifier according to claim 1, characterized in that the molecular weight of the oxypropylene unit in the compounds of structure I is 2600 to 3400. Field of application of the invention The invention relates to a demulsifier 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, 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 petroleum is the splitting of these primary promoted emulsions necessary cleavage systems, the emulsions in the temperature range of 20 ° C-85 ° C with the addition of 10-300ppm surface-active substances, demulsifiers, gospalten. 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 resin oxalkylates with dicarboxylic acids or their anhydrides, such as diglycolic acid and maleic anhydride. Oxalkylates of N, N "-tetra- (5-oxypropylpropylol) -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 alpha-methylstyrenediol or its polyglycol ethers Diurethane of the general formula