BG99351A - Deemulsifirer for oil dehydration and desalination - Google Patents

Abstract

The deemulfifirer (DOAE-20) is oxyethylated amidoesters of vegetable fatty acids (VFA) and monoethanolamine (MEA) having the general formula where R is alkyl radical having C14-22 and n means the number of oxyethelene links and is equal to 15 to 20. The deemulsifier is produced from VFA, MEA and ethylene oxide (EO) in two stages: preparation of VFA and MEA aminoesters and oxyethylation of the amidoesters produced in the first stage in the presence of catayst having alkaline properties, in particular potassium or sodium base. The deemulsifirer has the following composition in wt.%: FVA fraction with C14-22 from 10.5 to 17.6, MEA 0.9-1.5, EO from 18.6 to 30.9 and solvent, in particular toluene or benzene, or xylenes (o,p) or a mixture of diethyleneglycol and ethyl alcohol from 50.0 to 70.0. In 10 ppm concentration in oil having salts content of 82.6 mg/dm3, dehydration degree of 100% and desalination of 93.0% is achieved by mean of the deemulsifirer which enables it to be used in the treatment of high salt-containing petroleum.

Description

HEIT DEMOLGULATOR FOR DEMOLITION AND DESALATION

The invention relates to a non-ionic type demulsifier for dehydration and desalination of oil.

BACKGROUND OF THE INVENTION

Non-ionic types of demulsifiers for the dehydration and desalination of petroleum, which are oxyethylated amides (di ~, tri- or viscous amides) of fatty acids, are known, such as ethoxytriamide - PDE - 20/1 /, ethoxidiamide - 55/2 / and 2558 ethoxy high fatty acid amides (3).

Different amines have been used to synthesize the above demulsifiers: alkylentriamines (1), alkylenediamines (2) or polyamines (3).

The Procfainor 2558 demulsifier was prepared by the oxyethylation of synthetic fatty acid viscous amides, the number of Oxy0 'ethylene units being from 8 to 10. The commercial product is a solution in an aromatic solvent containing 45 X active mass (3). The demulsifier ethoxidiamide - 55 (2) was obtained by oxyethylation of the alkylenediamides of synthetic fatty acids, using ethylene - or hexamethylenediamines or waste containing them as starting amines, such as the carbamol production residue. It is distinguished by the number of oxyethylene units from 19 to 30. The commercial product is a solution of the synthesized product in isopropyl alcohol with an active mass content of 60> 70 I (2). The DEE-20/1 demulsifier is oxyethylated diethylenetriamides - synthesized from vegetable fatty acids and diethylenetriamine. The number of oxyethylene units is from 15 to 25. The commercial product is a solution in an aromatic solvent (toluene, methyl ether, metadad, n-butanol, 2-ethylhexanol) containing an active mass of 50% (1).

The EDE-20 emulsifier is characterized by the following composition: - a fraction of vegetable fatty acids ^with 14 - ^with 22 diethylenetriamine ethylene oxide toluene or methylethanol,

16.4 ♦ 26.2 I 1.8 f 2.8%

32.0 ♦ 51.0% or methanol or n-butanol or 2-ethylhexanol 20.0 ♦ 50.0 I and having the physicochemical parameters shown in Table 1.

Table 1 Physico-chemical parameters of the demulsifier RDE-20 and the active mass (a. M)

Indicators 100% a, and PIE-20 with 20% toluene 1. Relative density at 20 * 0 1.06 1.0 2. Viscosity at 50 ^w C, 63.0 60.0 3.Molecular mass 800 - 4. Cooling temperature, * With plus 8 minus 6 5.AMIN0 number,% 0, « 0.5 6. Water content, * percent percent 7. Surface tension of 1% solution - aqueous, ML7 39.1 - 8. PH of 10% aqueous solution 10.9 - 9.one number, / 100 ^ 42.6 **

The disadvantage of the demulsifiers described above is that they do not provide a sufficiently high degree of desalination and dehydration of oil.

TECHNICAL CbIHOCT OF THE INVENTION

It is an object of the invention to provide an effective and affordable demulsifier for dehydration and desalination of oil.

The essence of the invention is that as a demulsifier for dehydration and desalination of oil, oxyethylated amoesters of vegetable fatty acids (PMC) and monoethanolamine (MED) are used with both formulas:

H (CH ₂ CH ₂ O) _n ---- d-CH ₂ CH ₂ 00CR, where

OCR

R - alkyd radical having carbon numbers from 14 to 22 η - number of oxyethylene units and - equal to 15 4 20 and the following composition:

- a fraction of vegetable fatty acids

The starting materials for obtaining the proposed demulsifier for dehydration and desalination of oil are:

- vegetable fatty acids with carbon numbers of 14 to 22, which are the product obtained from the decomposition of Coagmock (the sludge that falls off after alkaline treatment of sunflower or soybean oils) with a mineral acid, called these free fatty acids.

- Monoethanolamine (IEA)

- ethylene oxide (EC)

The proposed demulsifier comes in two stages:

- Preparation of vegetable fatty acid amidoesters at 135 * 165 ⁱⁿ C for 2 * 4 hours at atmospheric pressure and in vacuo to a degree of conversion of PMC to their corresponding amidoesters not less than 99,0

- oxyethylation of the PMC amidoesters in the presence of a catalyst with alkaline properties - on a tris or potassium base (0.2 ♦% relative to the PMC amidoesters) at a pressure of 0.2 ♦ 0.5 MPa, • · · ·

- 4 temperature 135 * 175 ° C and process duration 4-6 hours.

The advantages of the present demulsifier for the dehydration and desalination of oil according to the invention are:

- a higher degree of dehydration and desalination of oil, resulting in improved quality of the petroleum products produced and reduced corrosion in the refineries.

- the use of monoethanolamine as an amine feedstock, thereby widening the range of feedstocks to produce demulsifiers.

The laboratory test for the evaluation of the demulsifying activity of the demulsifiers was carried out according to the methodology for thermostatic dehydration and desalination of oil, in the following tours to oil

90 ° C, washing water 7% vol., Concentration 15 ppm, time 5 4 180 min.

PRINCIPLES FOR IMPLEMENTING THE INVENTION

Example 1. Dehumidifier for dehydration with the following composition:

PMK fraction with C _1A - C ₂ 2 monoethanolamine ethylene oxide solvent toluene conditions: tempera demulsifier from and desalination of

17.6

1.5

30.9

50,0%

%%% is obtained in a batch reactor equipped with a stirrer in which, after a leak check, RMKs with carbon numbers of 14 to 22 in the amount of 0,176 kg are charged (the fat content calculated as oleic acid is required not less than 70%) and a MED in the amount of 0,0150 kg.

The mixture in the reactor is heated in indirect water vapor with continuous stirring to a temperature of 135 ° C, at which the process of condensation and esterification of PMK and copper begins, which takes place at atmospheric pressure, temperature 135 4 165 ° C, for 2 t 4 o'clock. The process ends with evacuation at a residual pressure of 0.015 4 0.035 MPa to a conversion rate of not less than 99.0% (the amine number of the obtained amidoesters is less than 1 I) have been demonstrated by IR spectroscopy and more important physic- Chemical Indications The obtained amidoesters are characterized by the following:

relative density at 20 ° C

0.940 ♦ 0.970

- viscosity at 50 ^e C, esi £ - 55 * 62

- molecular weight - 550 ♦ 650

- an amine number I not higher than 1

After cooling the reaction mass to temperature

Potassium base catalyst (0.5 * 1%) was dosed with 100'C into the reactor against the amidoesters and re-evacuated for 1/2 hour in order to remove the moisture introduced by the catalyst. The reaction mass was then warmed up, and when the temperature reached 120 ° C in the reactor, a metered delivery of ethylene oxide - 20 moles to the amidoesters was started with continuous stirring. Oxyethylation is carried out at a temperature of 135 * 175®C and a pressure of 0.2 * 0.5 MPa for 4 * 6 hours. The reactor was cooled to 40 * 50 ° C and the resulting product was dissolved with 0.500 kJ of toluene solvent.

Table 2 presents the physicochemical parameters of the active mass obtained and of the demulsifier C0AE-20), which is a solution in toluene with an active mass content of 50 l.

Table 2

High-chemical performance of demulsifier D0AE-20 and active mass (ppm)

100% D0AE-20 M Indicators am p 501 toluene 1. Relative density at 20C 1,050 th most common 0.948 2. Viscosity at 56 ° C 65 24.4 3. Molecular weight 900 - 4. Freezing point, ®C PLUS 14 mn ^ s 9 5. Amine number, 1 0.5 0.3 6. Water content,% percent percent 7. Surface tension of 11-aqueous solution, MD // ^ 40,0 - 8. pH of 10% aqueous solution 11 - 9. iodine number / 100 change -

Example 2. Oil demulsifier and desalination agent prepared as in Example 1 with the following composition:

RMC - 10.5 I

MEA - 0.9 t

EC - 18,6 I solvent toluene - 70,0%

Example>. Demulsifier for dehydration and desalination of oil, prepared as in Example 1, with the composition:

RMC - 17.6%

HONEY - 1.5%

E0I - 30,9 I solvent - (benzene or xyloi (o, p), or a mixture of diethylene glycol and ethyl alcohol taken in 1: 1 ratio) - 501

Example 4. The demulsifiable activity of solutions of the proposed demulsifier D0AE-20, obtained according to Examples 1 and 3, was investigated for the dehydration and desalination of oil of Russian export of laughing agent with an initial salt content of 82.6 / n ^ idwC. the results are shown in Table 3.

Example 5. The demulsifier for oil dehydration and desalination obtained according to Example 1 was tested in laboratory conditions for the demulsifying activity on oil as in Example 4 and compared with that of the EDE-20 demulsifier which is comparable to the Proc & inor and DiMofvan demulsifiers / 1 / .

Table 4 shows the results of the comparative tests * of DOAE - 20 and RDE - 20 demulsifiers.

From the above results in Table 4 it follows that at a concentration of 5 ppm of DOA - 20 in oil, the degree of dehydration is 92.8 I, which is 7.1 t higher than that of the demulsifier PDE 20 at the same concentration. The degree of desalination achieved with demulsifier D0AE-20 at a concentration of 5 ppm88,31 and 5,31 higher than that of PDE-20 under the same conditions.

At a concentration of 10 ppm, the degree of dehydration of the oil with demulsifier D0AE-20 is 100 and with the demulsifier RDE-20 is 92.8%, ie. 7.2 I lower than that of D0AE-20.

When comparing the degrees of desalination at a concentration of 10 ppm, it turns out that with the D0AE-20 demulsifier 93.0% is achieved and with the EDE-20 - 89.2 I desalination rate, ie 3.8% lower.

On the basis of the comparison, it is apparent that the proposed demulsifier having the composition of Example 1 has a higher demulsifying activity than that of the EDE-20 demulsifier.

Claims (2)

COPYRIGHT CLAIMS 1. Non-ionogenic type de-emulsifier for dehydration and desalination, the washed active mass is oxyethylated vegetable fatty acid amidoesters of the general formula: H (CH ₂ CH ₂ O) n-N ^/ - CH ₂ CH ₂ 00CR, where OCR β - alkyd radical * C ₂ 2 and - number of oxyethylene units equal to 15 * 20 2. The dehydrating and desalinating oil according to claim 1, contains an active mass and a solvent characterized by the following composition: - Vegetable fatty acid fraction of carbon atoms C ₂ -C ₂ 2 - monoethanolamine - ethylene oxide - toluene or benzene or xylene (o, p), or a mixture of diethylene glycol and ethyl alcohol 10.5 * 17.6% 0,941.5% 18.6 * 30.9% 50.0 * 70.0%