RU2024580C1 - Demulsifier for oil emulsion separation - Google Patents

Abstract

FIELD: oil industry. SUBSTANCE: demulsifier has, wt.-%: hydroxyethylated 2-bis-(γ-dimethylaminopropyl)-aminomethyl-4-isononylphenol of the general formula (I) (image) where n = 20-60 50-75 and ethyl alcohol 50-25. EFFECT: enhanced quality of demulsifier. 8 tbl

Description

 The invention relates to demulsifiers and can be used to separate oil emulsions with different water contents in primary oil preparation processes (at ELOU-AVT units), in the utilization of oil sludge stored in storage ponds ponds, as well as in the recovery of oil oils.

 For the separation of oil emulsions, demulsifiers based on blocks of a copolymer of ethylene oxide and propylene, as well as products based on acrylamide, are used. However, the use of demulsifiers based on blocks of copolymers of ethylene oxide and propylene and acrylamide is limited by the absence of raw materials, and their use requires additional equipment for the preparation of solutions of demulsifiers, which greatly complicates the technological scheme of the installation for processing oil emulsions (1).

^и

где R - алкильный остаток, содержащий 9-10 атомов углерода: n ≈10-12.These disadvantages are partially eliminated when non-inogenic surfactants based on alkyl phenols are used as demulsifiers. Such substances include the product OP-10, which is an ethoxylated mono- and dialkylphenols (2). The structural formula of OP-10 (conditional) is as follows:

^and

where R is an alkyl residue containing 9-10 carbon atoms: n ≈10-12.

 This product is accepted as a prototype.

The disadvantages of demulsifiers based on alkyl phenols are as follows:
to achieve a sufficiently high efficiency of demulsifiers, the content of ethylene oxide in them at the level of 80-85% is necessary;
they can only be used to demulsify a small number of oil emulsions, because are not universal.

 The purpose of the invention is to increase the efficiency of demulsifiers based on ethoxylated alkyl phenols used in the separation of various types of oil emulsions.

где n = 20-60, а в качестве растворителя применяют этиловый спирт, при этом компоненты деэмульгатора взяты при следующем соотношении (мас.%): Оксиэтилированный 2-бис-( γ-диметилами- нопропил)-аминоме- тил-4-изононилфенол 50-75 Этиловый спирт 50-25
Деэмульгаторы с различной степенью оксиэтилирования получали на основе препарата ФОМ-9 - фенольного основания Манниха, синтез которого осуществляли следующим образом, а именно к 220 г (1 моль) нонилфенола при 25-30^оС добавляли 136 г (1 моль) тетраметилдипропилентриамина (ТУ 38-502-48-83), и постепенно добавляли 160 г (1 моль) 30% формальдегида и перемешивали 2 ч при 70-80^оС. После подсоединения вакуума и отгонки воды при 80-100^оС при 200 мм рт.ст. получали 350 г (95%) целевого продукта, представляющего светлую жидкость мол.м. 410 (М_ср) и аминным числом 267.This goal is achieved by the fact that when separating various types of oil emulsions, a demulsifier is used, including ethoxylated alkyl phenol and a solvent, while ethoxylated 2-bis (γ-dimethylaminopropyl) aminomethyl-4-isononylphenol of the general formula

where n = 20-60, and ethanol is used as a solvent, and the components of the demulsifier are taken in the following ratio (wt.%): Ethoxylated 2-bis- (γ-dimethylamino-propyl) -aminomethyl-4-isononylphenol 50 -75 Ethyl alcohol 50-25
Demulsifiers with various degrees of ethoxylation was prepared based on the preparation FOM-9 - phenolic Mannich bases, the synthesis of which was performed as follows, namely to 220 g (1 mol) of nonylphenol at 25-30 ^{° C} was added 136 g (1 mol) tetrametildipropilentriamina (TU 38 -502-48-83) and gradually added 160 g (1 mol) of 30% formaldehyde and stirred for 2 hours at 70-80 ^C. After the vacuum connection and distillation of water at 80-100 ^{° C} at 200 mm Hg received 350 g (95%) of the target product, representing a clear liquid mol.m. 410 (M _cf ) and an amine number of 267.

Oxyethylation Mannich base (FOM-9) 38407343-86 TU-etoksilatore led into the reactor at 60-80 ^{° C} in the absence of a catalyst.

 1 mol of FOM-9 was loaded into the reactor, the reactor was purged with nitrogen, 4, 20, 60 moles of ethylene oxide were added respectively. The reaction mass was held for 30 minutes, unloaded and analyzed by amine number and molecular weight.

 Indicators of ethoxylated FOM-9 are given below.

Molecular amine
mass M _cr number (mg
HCl per 1 g
product) FOM-9-4 595 184 FOM-9-20 1299 84 FOM-9-60 3059 36 FOM-9-80 4039 12
The effectiveness of demulsifiers was evaluated on a model emulsion of the oil-water type, as well as on real oil sludge systems selected from the top and bottom of the sludge collector.

The preparation of the oil-water emulsion was carried out according to the modified Kremnev method. A wire spiral was released into an open graduated cylinder containing 20 cm ^{3 of} water, with which emulsification was carried out. The spiral had 3-5 turns, the diameter of the largest turn being less than the diameter of the cylinder in which the emulsion was prepared. Oil from the burette was released in drops at a certain rate so that it drained along the walls of the cylinder. The speed of the spiral was in accordance with the speed of oil supply from the burette and so that it had time to continuously disperse and not accumulate significant volumes on the surface of the emulsion. When the concentration of oil in the emulsion reached 80 vol.%, The flow of fluid from the burette was stopped and the spiral movement ended.

Petroleum oil was taken as an object for research, having the following characteristics: density ρ ₄ ²⁰ , kg / m ³ 878.6; ν ₅₀ , mm ² / s 18.3; content of mechanical impurities,% 1.2; flash point in a closed crucible, ^о С 154. The composition of the hydrocarbon part of petroleum oil was determined by chromatography on silica gel, wt.%: paraffin-naphthenic 74.40; monoaromatic 20.80; biaromatic 2.90; triaromatic 1.30; tar 0.60.

 All further determination of the activity of demulsifiers was carried out for emulsions containing water in an amount of 20 vol.%.

 The objective function (K) is a parameter defined as the ratio of the volume of water extracted from the emulsion to the source water in a shared emulsion.

The effectiveness of demulsifiers was determined by centrifugation and sedimentation. When using the method of sludge process temperature was varied from 20 to 80 ^C. The concentration of demulsifiers was used 100 to 500 mg / l.

 The results for determining the effectiveness of demulsifiers are given in table. 1-4.

 As can be seen from the table. 1-4, when separating emulsions of the oil-water type, the demulsifiers of the FOM-9 series with different degrees of hydroxyethylation are superior to the demulsifying ability of OP-10.

In the table. 5 on the example of demulsifiers FOM-9-20 and FOM-9-60 presents the results on the influence of the composition of the solvents on the effectiveness of the demulsifiers series FOM-9 in the separation of oil emulsions at a temperature of 80 ^about C. As solvents used water, isopropyl and ethyl alcohols and a mixture of isopropyl alcohol and water taken in a ratio of 50:50 vol. % The concentration of demulsifiers was 50 wt.%. Demulsifiers in a solution of ethyl alcohol are more effective than demulsifiers based on isopropyl alcohol, water and a mixture of isopropyl alcohol and water.

 The effectiveness of demulsifiers was also determined in the separation of oil sludge processed at the Ryazan and Kirish refineries.

 The characteristics of oil sludge are given in table. 6.

 Preliminary tests showed that with a RPM of 6000 and an exposure time of 5 min, the separation of the Ryazan oil sludge did not occur. Only the introduction of demulsifiers into oil sludges contributed to the release of water from the oil emulsion.

 As an estimated indicator, a parameter was adopted - the degree of water release from the sludge, defined as the ratio of the amount of released water during separation by centrifugation to its potential content in the oil sludge. To assess the effectiveness of the FOM-9 demulsifiers, we used imported demulsifiers Proestol-665BC and Accofloc-100 based on acrylamide, the domestic Metacid product based on polyhexamethylene guanide inhydrochloride and Diproxamine, a block copolymer based on ethylene diamine. Demulsifiers of the FOM-9 series (Tables 7 and 8) are superior in efficiency to domestic and foreign demulsifiers in the separation of oil sludge from the Ryazan and Kirish oil refineries.

 Oil sludge from the Kirishi oil refinery, taken from the top of the oil trap, had a higher degree of water cut (86%) than from the Ryazan oil refinery and was divided into the water and hydrocarbon parts during sedimentation. The results on the effect of demulsifiers on the degree of separation of oil sludge from the Kirishi refinery are given in table. 7.

 Accofloc-100, Proestol-665BC, Metacid was used in the form of aqueous solutions, and Diproxamine was dissolved in isopropyl alcohol, PO-10 in water, and FOM-9-20 in ethanol.

 Thus, the FOM-9 preparation with a degree of hydroxyethylation of 20-60 is an effective demulsifier for the separation of various types of oil emulsions.

Claims (1)

A demulsifier for the separation of oil emulsions containing ethoxylated alkyl phenol, characterized in that, as ethoxylated alkyl phenol, the demulsifier contains ethoxylated 2-bis (γ-dimethylaminopropyl) -aminomethyl-4-isononylphenol of the General formula

where n = 20 - 60,
and additionally contains methanol as a solvent in the following ratio of components, wt.%:
Oxyethylated 2-bis (γ-dimethylaminopropyl) -aminomethyl-4-isononylphenol 50 - 75
Ethyl alcohol 25 - 50

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