SU1031972A1 - Block-copolymer based on isobutylene and ethylene oxide as deemulsifier for crude oil - Google Patents

Abstract

A block copolymer based on isobutylene and athene oxide with the general formula H- (o-CH, -. CH8J-0-j | -CHz- ОR (® "rfe" - -o- (OHj-aij-o). And gdvB1vr "5 - 20; | .15 - 26, as a demulsifier for oil. W

Description

The invention relates to new chemical compounds, namely to the synthesis of block copolymers of isobutylene and ethylene oxide, which can be used as demulsifiers in the preparation of oil for processing.

Anionic, cationic and non-ionic surface-active substances (SAS) are used for dehydration and desalinization of oils. The following surfactants are known to be used as demulsifiers: sodium salts of monoethanolamide phthalates of capric lauric, myristic and palmitic acids, sodium salts of monoesters of orthophthalic acid and synthetic fatty alcohols t 1 ton of oil).

Of course, it is used as a polyurethane demulsifier obtained by reacting a hydroxyl-containing block copolymer of ethylene oxide and propylene oxide with toluene diisocyanate 23.

The known compounds are used for dewatering and desalting oil with a water content of up to 20%.

A disadvantage of the known demulsifiers is the complication of the desalting stage, the use of elevated temperature -. exposure to electric field), use for its synthesis of deficient - propylene oxide. In addition, it is known to use as a desmulsifier an imported reagent brand Dissolvan 4411, which is a 65% solution of nonionic surfactant in methyl alcohol (its formula is unknown), a domestic demulsifier brand Diproxamine - 157, which is a block copolymer of ethylene oxide and propylene oxide based on ethylenediamine H.

However, these demulsifiers have insufficient demulsifying ability — they do not provide sufficient dehydration of oil. They work well only at temperatures of 40 -, which leads to the need to load the extracted oil.

. The closest in structure to the proposed are ethoxylated fatty acids (OHA) of the general formula

(CNG-SNG-0) „N o

where R is the hydrocarbon radical of the fatty acid, and n 7 - 20, otherwise, and n 7 20 4.

However, the demulsifying efficiency of the ethoxylated fatty 5 acids is low: at a dehydration process temperature of 60 ° C and at a suction time of 4 hours, a degree of dehydration of 91–93% is achieved.

The purpose of the invention is the pseudation of new chemical compounds with a demulsifying ability and providing a high degree of dehydration and high speed of the process at room temperature. These properties are determined by the new chemical structure of the block copolymer based on isobutylene and ethylene oxide, which is expressed by the following general formula

0 n- (o-CH2-CH2) 0-C-CHg CH5 C%

5 "4 N-s-o- (eng-CH g - o n o

where t-: - 5 - 20;

P 15 - 26. These copolymers receive

0 by oxyethylation of oligoisobutylene with finished carboxyl groups at 160-180 for 8-20 hours in the presence of an alkaline catalyst.

5 P and measures 1. Hydroxyethylation is carried out at atmospheric pressure. 30 g (0.03 g-mol) of oligo-isobutylene with terminal carboxyl groups (DECG) are placed in a flask at

Q p 15 and 0.2 g (0.0035 g-mol) of potassium hydroxide as a catalyst. The contents of the flask are heated and at 160 or ethylene oxide is fed into the flask with continuous stirring of the reaction mixture. KB5 the amount of ethylene oxide added is determined by the weight gain, in this case it is 13.58 g (0.31 g-mol) and corresponds to .. The product yield is 43.58 g

0 100%. Mopecul ria mass M 1412. Vrutto formula

Ss-ve -

Calculated,%: C 72.2; H 11.9. Found,%: C 72.0; H 12.1.

5 Example 2. The synthesis was carried out as described in Example 1. The amount of DECG (p. 15) was 30 g (0.03 g-mol) in the reactions, the amount of ethylene oxide added was 21, 72 g (0.49 g -mole), which corresponds to .. The product yield is 51.72 g, 100%, 1676. Gross formula

Calculated,%: C 69.4 N 11.5.

Found,%: C 69.1; H 11.8.

Example 3. Synthesis was carried out similarly to that described in Example 1. The amount of DECG (l 15), taken into reaction, is 3Q g (0.01 gmol), the amount of ethylene oxide added is 32.6 g (0.74 g g-mole) that corresponds. Product yield 6, b g 100% 7 A „, 2028. Bruttog formula

In | number,% s With 66.9; H 11. “found,%:, i; H 10.8.

; tn p. and meper T .. The synthesis was carried out as described in Example 1. The amount of DECG (p. 20) taken in the reaction was 30 g (g-mol), the amount of ethylene oxide added was 12.65 (O, 29 g / July), corresponding to

. Yield prprdu | st; a 42.65 g 100Vit. Ats 1780. Gross formula

Fiitcjietio,% C 73.4J H 12.1. : itdflweRa /% t С 73/1; In 12.5. p 5, Synthesis of 5klok with ") pazayulbu A of eobutylene and ethyl oxide and on ma1 ecula | It has a mass of isobutylene chain 1252, which corresponds to p 20, and an ethylene oxide content of 41.2% based on the final product.

/ Synthesis is carried out similarly as described in P | Even 1. The number of OIKR; Taking into account the reaction, it is 30 g (O, 023 g-mol), the amount of the product is 21/1 g (0.48 g-ml), which corresponds to (.j. Yield 51.1 g 100%, 2132. Gross formula

V

g

%: s 70, s; H 11.6. Naidio,% j from 70, o; n 11.9. P jp 8 ME 6. The synthesis is carried out in the manner described in the example. 1. The amount of DECG (p. 20) taken in the reaction is 30 g (0.02E g-mol), the amount of ethylene oxide added is 33.73 g (0.7 g of g-mol), which corresponds. The product yield 63,73 g, № «« 2660. Gross formula

S4

Calculated,% t with 67.20 H 11.1. Found,%: C 67.0; H 11.4. Example 7i Synthesis of a block copolymer of isobutylen and oxide, ethylene with a molecular mass of isobuty: a 1588 chain, which corresponds to pe 26, and an ethylene oxide content of 30.7% based on the final product. .

The synthesis is carried out as described in Example 1. The amount of HECH taken in the reaction is 30 g (0.019 g-mol), the amount of ethylene oxide added is 13.29 g (0.30 g-mol), which corresponds. The product yield of 43.29 g 100%, Mi 2292. Gross formula

5 Calculated,%: C 73.8; H 12,, 2. Found,%: C 74.0; H 11.9. Example 8. The synthesis was carried out as described in Example 1. The amount of DECG (p 26) per reaction; was 30 g (0.019 g-mol), the amount of ethylene oxide added was 21.6 g (O, 49 g - mole), which corresponds. The yield of the product is 51.61 g: 100%, 2732. Vulla formula 5..

Calculated,%: 70.7 | H 11.7. . Found,%: C 71.0; 11.5.

Example 9. Synthesis of a block copolymer of isobutylen and ethylene oxide with a molecular weight of the isobutylene chain of 1588, which corresponds to n 26, and an oxide content

5 ethylene 52.6% based on the final product.

The synthesis is carried out as described in Example 1. The amount of DECG taken in the reaction is 30 g (0.019 g-mol), the amount of ethylene oxide added is 33.23 g (0.75 g-mol), which corresponds to f. Product output 63.23 g iOO%, / iAy, 3348. Gross Emulsion

five

89% Calculated,%: C 67.7; H 11.2.

Found,%; C, 67.4; H 11.4. 0 The structure of the new compounds is proved by NMR-H-spectroscopy data. On the NMR-H spectrum, resonant signals of protons of the following groups are observed:

5 | I

- С- «СНзс by the Chikshich shift of CHj. -1,25 ppm

chemical shift

-O-CH 3.55 ppm

with chemical shift (m4 --on

4.05 m; d. The spectrum is recorded on an O device with an operating frequency of 80 MHz. Vlob copolymers of isobutylen and ethylene oxide

when n 15 and 5 have a weak demulsifying ability. Block copolymers of isobutylene and oxide; ethylene at 2b and 20 do not differ in their demulsifying activity from the proposed block copolymers. However, taking into account that to obtain block copolymers m i: i 2t) a significant amount of ethylene oxide is required, the upper limit is limited by the values of and.

Example 10. Testing the de-emulsifying ability of a block copolymer of isobutylene and ethylene oxide is carried out on a natural emulsion of Romashka oil according to the procedure recommended by the Giprovostokneft institute.

For comparison, water growing was selected. Imported dissolvan brand 4411 was imported.

To 150 ml of a water-in-oil emulsion was added a 1% solution of a block copolmer of isobutylene and ethylene oxide in a mixture of toluene and isopropanol, taken in a ratio of 3: 1 and mixed with em. For 10 minutes. Then, the treated oil is settled in a water bath for 2 hours, with a volume of settled water every 0.5 h.

Example a. When testing the demulsifying ability of the block copolymers of isobutylene and ethylene oxide at an oil reflux temperature, stirring is carried out for 60 minutes. Under similar conditions, imported dissolvan 4411 and domestic diprocchiamine 157 are tested. The demulsifying capacity data for the block copolymers of isobutylene and ethylene oxide are presented in Table. one.

The test results are shown in Table. 1, it can be concluded that the block copolymers of isobutylene and ethylene oxide by their demulsifying capacity are superior to the imported dissolvane 4411 reagent, the domestic diproxil 157 reagent and the known hydroxyethyl acids (fatty acids with the number of carbon atoms from 7 to 20 and more than 2D. The use of block copolymer iobutylene and ethylene oxide as deemulgators provides 100% dehydration

oil, which eliminates the need to heat the oil produced.

The advantage of block copolymers of isobutylene and ethylene oxide is that when they are obtained, propylene oxide is not required in our country, unlike other proposed demulsifiers, such as diproxMina 157.

For comparison, the proposed demulsifiers with known 2, which have a desalting and dehydrating effect, are given and tab.

The dewatering conditions are the same as those in Example 10 Stabl.2K. The order and conditions for testing the desalting capacity of block copolymers of isobutylene and ethylene oxide (Table 3) are followed: to the previously dehydrated oil containing 0.5% water, the demulsifier from calculate 27-32 g / t of oil, 8 ml of distilled water and mix for 1 min (mixing intensity 4 UOO rpm). After mixing the oil sample, stand in a water bath for 30 minutes at 50 ° C. Free water is then removed, and residual water and chloride salts are determined in samples of the treated oil.

It is known that when desalting oil, the temperature setting from 50 s to. Results in a decrease in demulsifier consumption by 7 g / t. Consequently, the consumption of the proposed demulsifier at the desalting stage at 65 ° G will be 20-21 g / t. In addition, the use of an electric field also leads to a decrease in the consumption of the demulsifier. Thus, the use of the proposed demulsifiers simplifies the technology of the desalting stage of fti, since the use of an electric field increases the cost and complexity of the oil preparation process, in addition, the increased temperature leads to the loss of low boiling oil fractions, which are valuable petrochemical raw materials.

Thus, the proposed demulsifiers have a high demulsifying effect and simplify the preparation technology.

oil for processing.

T a b l i

U a

Blick copolymers of isobutylene and ethylene oxide with different values of p and

BLOCK copolymers of oootilev and ethylene oxide with different values of n

t, p Characteristic of oil used dp Ox content:% 19 Content of chloride salts, mg / l 40000

ten

1031972

continuation of the table. one

F a b and c tests on spoooo

Data is collected from 23.

Table 3

Claims (1)

A block copolymer based on isobutylene and ethylene oxide of the general formula H- (O-CH, -CH ₂ ) -O - ^ - CHg№ 5®. “H ^“ 7 “O) -N <%} O ^P where and "p" 5 - 20; Y "15 - 26, as a demulsifier for petroleum. one 1031972