The method of obtaining the demulsifier for breaking oil-water emulsions
(57) Abstract:The invention relates to a method for the demulsifier for breaking stable emulsions formed heavy resinous oils. The method consists in the condensation of alkylphenol or dialkylphenol, where alkyl WITH4-C30and formaldehyde in the presence of an acidic catalyst by heating in a molar ratio alkilirovanny phenol: formaldehyde = 1:(0,8-1,2) with subsequent oksietilirovannye product of condensation to the content of hydroxyethyl groups in the resulting product 30-70 wt.%. Formaldehyde is used in the form of its solution in methanol, in the form of formalin or proforma. Effect: effective demulsifier with the inhibiting effect of asphaltene-resin-paraffin deposits. 1 C.p. f-crystals, 2 tab. The invention relates to a method for demulsifying agent, which can be used to destroy stable oil-water emulsions formed of resin and paraffin oil.A method of obtaining the demulsifier for breaking oil-water emulsions, comprising the condensation of formaldehyde and phenols extracted from shale resins, followed oxyethylene, 1967, S. 133].A method of obtaining the demulsifier for separating oil emulsions, comprising the condensation of phenol and formaldehyde, oxypropylene product of condensation with subsequent interaction with the ethoxylated polypropylenglycol [Patent USSR 1209034, MKI 08 G 8/28, 1986].However, the emulsion obtained by these methods have low efficiency in relation to water-oil emulsions of heavy and resinous oil.Closest to the invention is a method of obtaining the demulsifier for breaking oil-water emulsions [RF Patent 2037511, 6 To 10 G 33/04, 1992. ] including condensation of alkylphenol with 4-12 carbon atoms in the alkyl chain with high-boiling by-product of the production of isoprene from isobutylene and formaldehyde or from 4.4-dimethyldioxanes in the presence of an acidic catalyst, oxoethylidene the obtained condensation product of dostizheniya of hydroxyethyl groups in the resulting product oksietilirovannye 30-70 wt.%.However, the demulsifier obtained by this method exhibits good dewatering and desalting capacity after a longer period of time, and not very effective against water-oil emulsions heavy is of isoprene from isobutylene and formaldehyde - multi-component product that contains about 50% of the reactive dioxane alcohols and ethers, and not having a constant ratio of these components, which may affect consumer properties of the resulting demulsifier.The present invention is the task of developing a method of obtaining an effective demulsifier for breaking stable emulsions formed of resin and paraffin oil, with the effect of inhibiting asphaltene-resin-paraffin deposits.The problem is solved so that the method of obtaining the demulsifier for breaking oil-water emulsions derived by condensation of phenol and oxygen-containing component in the presence of an acidic catalyst by heating with subsequent interaction of the obtained product with ethylene oxide, as a derivative of phenol using monoalkylphenol with the number of carbon atoms in the alkyl radical WITH4-C30or mix it with dialkylphenols with the number of carbon atoms in the alkyl radical WITH4-C30and as the oxygen-containing substance use formaldehydefree product at a molar ratio derived fste of monoalkylphenols with the number of carbon atoms WITH4-C30in the alkyl moiety can be used, for example, isooctylphenol on THE 6-14-579-E or isononylphenol on THE 38.602-09-20-91. As dialkylphenols can be used, for example, 2,6-di-tertbutylphenol on THE 38.103378-86.As formaldehydefree product use water or water-methanol solution of formaldehyde, or paraform. An aqueous solution of formaldehyde - formaldehyde is used in accordance with GOST 1625-89 "Formalin technical", perform in accordance with THE 6-09-141-03-83 "Paraformaldehyde", water-methanol solution of formaldehyde in accordance with THE 38.602-09-43-92 "Formaldehyde methanol".As a solvent, the composition may contain, for example, a mixture of aromatic hydrocarbons - nefras Ar 120/200 on THE 38-101-809-90, or butylbenzene fraction (BBF) TU 38.10297-76, or alcohols: methanol, or isopropanol according to GOST 9805-84, or their mixtures with water, or a mixture of aromatic hydrocarbons with alcohols and C2-C4- monoalkylamines esters of ethylene and diethylenglycol. As C2-C4- monoalkyl ethers of ethylene and di-etilenglikola use monotropy ether of ethylene glycol (MEEEH) - ethyl cellosolve according to GOST 8113-88, or monotropy broadcast detiling THE 6-05-10-5086.Ethylene oxide used according to GOST 7568-88.The condensation process are known manner of interaction of a derivative of phenol with formaldehyde when heated in the presence of an acidic catalyst. As acidic catalysts can be used, for example, sulfuric acid or organic sulfonic acids, such as benzosulfimide or alkylbenzene-acid, or sulfonic cation, or anhydrides of organic acids, such as maleic anhydride or phthalic anhydride or succinic anhydride in the amount of 0.5-1.5 wt.% from the reaction mass. The molar ratio of alkyl phenol: formaldehydefree product 1:(0,8-1,2), respectively.The resulting condensation product will exitresult to content oxyethylene groups in the product of 30-70 wt.%
Oxyethylated condensation product are dissolved.A new set of claimed essential features will allow you to get demulsifiers, effectively destroying stable oil-water emulsions, especially heavy and resinous oil.The analysis selected in the search process known solutions showed that in science and technology there is no object, having declared a mix of attributes, and which would lead to the indexes of "novelty" and "inventive step".To prove compliance of the proposed solution the criterion of "industrial applicability" cited specific examples of the preparation of demulsifier.Example 1. (The prototype). The reactor is placed 220 g (1 mol) of isononylphenol and with stirring was added dropwise a 1.46 g (0.5% of the reaction mass) benzosulfimide. Then poured 200 g of toluene or nefras And 120/200 and 73 g (0.5 mol) of the runway, gradually raise the temperature in the flask to 150oWith and simultaneously carrying out the distillation of water.After the distillation of water in the reaction mass is added 10 ml of a saturated solution of alkali. Oxoethylidene carried out in a conventional autoclave method.Example 2 (proposed). The reactor is placed 220 g (1 mol) of isononylphenol 81 ml of 37% technical formalin (1 mol of formaldehyde) of 1.25 g (0.5% of the reaction mass) benzosulfimide. Then poured 400 g nefras And 120/200 and warm for 3-4 hours at boiling point.After this time gradually raise the temperature in the flask to 150oWith and simultaneously carrying out the distillation of water. After the distillation of water in the reaction mass is added 10 ml of a saturated solution of lye.Oxoethylidene carried out in a conventional autoclave metasomatism analogously to example 2, changing the source reagents and their molar ratio in accordance with table.1.Example 50. The reactor is placed 275 g of a mixture of mono - and diisononylphthalate in the ratio of 1 mol and 0,2 mol respectively 89 ml 37% technical formalin (1.15 mol of formaldehyde) 1,82 g (0.5% of the reaction mass) benzosulfimide. Then poured 400 g nefras And 120/200 and warm for 3-4 h at the boiling point.After this time gradually raise the temperature in the flask to 150oWith and simultaneously carrying out the distillation of water. After the distillation of water in the reaction mass is added 10 ml of a saturated solution of lye.Oxoethylidene carried out in a conventional autoclave method.Examples 51-61 carried out analogously to example 2 by changing the initial reagents and their molar ratio in accordance with table.1.The resulting product is a viscous liquid from dark yellow to dark brown. Kinematic viscosity of 50% solution in nerase at 20oC is not more than 60 mm2/c. The density of 50%-aqueous solution of nerase at 20oWith, within 910-1105 kg/m3. Qualitative and quantitative composition of the products are given in table. 1.Received d the s on demulsifying activity and are shown in table 2. Testing of the samples for demulsifying activity carried out on the natural emulsion, oil field, oil which contains asphaltenes, resins and waxes in the following ratio: benzene resin 15,00-16,00%; alcohol-benzene resins 5,50-7,00%; asphaltenes 3,10-4,00%; paraffin 2,00-4,50%; oil density4200.88 to 0.90 percent; sulfur content, % 1,00-3,00%; water content 68,00-88,00%.Test method
The emulsion is metered into the emulsion in the form of a 1% solution in a mixture of toluene and isopropanol, taken in the ratio of 3:1. In natural emulsion injected demulsifier, the mixture shaken on a laboratory shaker Wagner for 30 min with an amplitude of 6-7 cm and a stroke rate of 120 per minute. At room temperature. Then termostatic for 2 h at a temperature of 20oTo measure the amount of released water.The determination of the content of residual water in the oil is carried out in accordance with GOST 14870-77 method Dean-stark.The results of the tests are presented in table.1 and 2.The demulsifier have on the efficiency of inhibition asphaltene-resin-paraffin deposits (ARPD).The effectiveness of preventing asphaltene-maloperation allogenicity.3. To launder ARPD.Determination of washing the oil film is carried out in the following order. In a glass tube to a certain label pour the oil treated with the reagent from the calculation of 0.005% on an active basis and stand for 20 minutes and Then the oil was poured in a test tube halfway pour produced water, add oil up to the mark. The tube is closed refinished tube, and then simultaneously turn on the stopwatch test tube is turned. Oil and water are changing volumes. Record the area of washing the surface of the tube occupied by the reservoir with water instead of oil. The result is excellent, if when 70% of the area is over 30, good for 60 s and satisfactory for 180 C.The dispersion of paraffin and washing the surface. These two methods are combined in one procedure and are carried out in a conical flask, which is placed 50 cm3produced water, dispense the test reagent. In the same flask ASPO weighing 0.5 g of the Contents of the flask are heated to melt the wax (60-90oC) and then cooled while stirring. After cooling to 20-25oTo measure the particle size of the dispersion of the wax and the surface area of the flask, covered (daubed) partynational (s).The compositions of the demulsifier and the results of their testing are given in table. 1 and 2.Analysis of the data presented in table.1,2, shows that the proposed method allows to obtain an effective demulsifier for breaking stable emulsions of resinous and waxy oils that have simultaneously the effect of inhibiting paraffin. 1. The method of obtaining the demulsifier for breaking oil-water emulsions by condensation of alkylphenol and oxygen-containing component in the presence of an acidic catalyst by heating with subsequent interaction of the product of condensation with ethylene oxide, characterized in that as the alkylphenol used monoalkylphenol with the number of carbon atoms in the alkyl radical WITH4-C30or mix it with dialkylphenols with the number of carbon atoms WITH4-C30in the alkyl radical, and as the oxygen-containing component is used formaldehyde as formalin, or proforma, or in the form of water-m is,2), and oxoethylidene condensation products of lead content oxyethylene groups in the final product 30-70 wt. %.2. The method according to p. 1, wherein the obtained product is added an organic solvent.
FIELD: crude oil treatment.
SUBSTANCE: to oil emulsion is added surface-active demulsifying additive containing (i) aqueous solution of surfactant based on sodium salt of oxyethylated isononylphenol carboxymethylate expressed by general formula C9H19-C6H4-O-(-CH2-CH2O)nCOONa, where n=10-12, (ii) self-emulsifying organosilicon compound, and (iii) sodium or calcium chloride salt.
EFFECT: increased demulsifying power.
1 tbl, 13 ex
FIELD: composition for crude oil treatment in oil producing and oil refinery industry.
SUBSTANCE: claimed composition is obtained by mixing of four components. Oxyethylated isononylphenone sodium carboxymethylate of formula C9H19-C6H4-O-(-CH2-CH2O)nCOONa, where n = 12 is used as an active ingredient. Silicone is introduced in composition as self-emulsifying addition, and aqueous or aqueous-salt solution is used as solvent. Composition contains (mass %) oxyethylated isononylphenone sodium carboxymethylate 25-35; self-emulsifying silicone addition 0.01-1.0; calcium chloride 0-25; and as balance: water.
EFFECT: composition with high demulsifying action and reduced foaming formation in crude oil emulsion.
2 ex, 1 tbl
FIELD: crude oil treatment.
SUBSTANCE: invention is directed to treatment of crude oil before processing by destroying persistent oil-water emulsions, dehydration thereof, and desalting with various-purpose demulsifier. Preparation of the latter involves preliminary oxypropylenation of nitrogen-containing compound (etylenediamine, tetramethylenediamine, hexametylenediamine, or polyethylene-polyamine) on heating. Resulting mixture is subjected to further oxypropylenation and then oxyethylenation in presence of alkali catalyst on heating. Thus obtained demulsifier is finally dissolved in solvent at weight ratio (45-55):(55-45).
EFFECT: increased efficiency in destruction of oil-water emulsion and in removal of petroleum products from waste waters accompanied by good corrosion protection and anti-deposits effect.
2 cl, 3 tbl, 20 ex
FIELD: oil and gas production.
SUBSTANCE: invention relates to pre-processing treatment of crude oil, in particular to dehydration and desalting of oil before transferring it into collection and transportation system for paraffin-rich oils. Invention provides for preparation of efficient formulation , which contains 20-75% of glycerol-based ethylene oxide/propylene oxide block copolymer, 2-10% of nonionic surfactant ("Dossolvan"), additionally 4-20% of product obtained by reaction of above block copolymer with toluene diisocyanate, 0.5-2.5% of oxyethylated fatty acid-based amine ("Oksamin-15") or product of reaction thereof with phosphorus-containing compound ("Oksamin-F 15"), and solvent to 100%.
EFFECT: increased efficiency in protection of oil-field equipment against corrosion and asphaltene-tar-paraffin deposits and enabled and enabled simultaneous treatment of waste water to remove oil derivatives.
2 tbl, 16 ex
FIELD: oil and gas production.
SUBSTANCE: invention relates to pre-processing treatment of crude oil, in particular to dehydration and desalting of oil with the aid of surfactant additives. Composition of invention contains 15-17% glycerol-based ethylene oxide/propylene oxide block copolymer, 5-15% oxyethylated glycerol/toluene diisocyanate reaction product, additionally oxyethylated fatty acid-based amine ("Oksamin-15") or product of reaction thereof with phosphorus-containing compound ("Oksamin-F 15"), and solvent to 100%.
EFFECT: increased efficiency in protection of oil-field equipment against corrosion and asphaltene-tar-paraffin deposits and enabled and enabled simultaneous treatment of waste water.
2 tbl, 16 ex
FIELD: crude oil treatment.
SUBSTANCE: objective of invention is treatment of crude oil before processing, in particular dehydration, desalting of oil, destruction of water-oil emulsions, and improvement of rheological properties to facilitate transportation of oil through crude oil lines. Composition contains 25.0-55.0% of nonionic demulsifier, notably ethylene oxide/propylene oxide block copolymer based on monoethylene glycol with average molecular mass 4300, 5.0-75.0% of diethylene glycol production distillate (including 20.0-40.0% ethylene glycol methyl ether, 30.0-60.0% diethylene glycol methyl ether, 2.0-5.0% methanol, and 15.0-18.0% water), and solvent, preferably methanol (to 100%).
EFFECT: enhanced oil dehydration and desalting efficiency and improved rheological properties of oil.
1 dwg, 2 tbl
FIELD: crude oil treatment.
SUBSTANCE: polymer-containing trapped emulsion is pumped from earthen container into settler containing fresh industrial water to obtain emulsion-to-water volume ratio 1:2. Resulting mix is heated via circulation through heat-exchange to 70-80°C while simultaneously receiving demulsifier in amount 20-50% of its estimated amount and aqueous solution of active chlorine-releasing compound in amount corresponding to 0.2-0.4 kg active chlorine per 1 m3 trapped emulsion. Hot trapped emulsion is then pulped to section of dispersers disposed in tubes supplying fresh industrial water preheated to 40-50°C while simultaneously feeding the rest of demulsifier to pump pumping trapped emulsion observing emulsion-to-water volume ratio (1-2):9. Dispersing cycle is repeated at least twice while draining after each cycle separated water. Finally, inverted emulsion is settled to residual water content 1%.
EFFECT: increased emulsion destruction efficiency due to increased degree of oil dehydration and lowered concentration of suspended impurities.
FIELD: chemical technology.
SUBSTANCE: invention relates to agents used in destruction of aqueous-petroleum emulsions and can be used in dehydrating petroleum in industrial units in petroleum preparing. The composition for destruction of aqueous-petroleum emulsions and treatment of sewage waters comprises dimethyl phosphite, nitrogen-containing compound, non-ionogenic surface-active substance, Phosphenox H-12, solvent and alkylbenzene sulfoacid in the following ratio of components, wt.-%: dimethyl phosphite, 0.01-2.0; nitrogen-containing compound, 0.2-2.0; non-ionogenic surface-active substance, 25.0-70.0; Phosphenox H-12, 1.0-15.0; alkylbenzene sulfoacid, 0.1-15.0, and solvent, the balance. Invention provides the development of effective de-emulsifying agent of aqueous-petroleum emulsion showing the complex effect for high-viscous oils.
EFFECT: improved and valuable properties of composition.
3 tbl, 20 ex
FIELD: crude oil treatment.
SUBSTANCE: oil emulsion is preliminarily separated from drainage water and, after addition of demulsifier, oil desalting process is carried out by washing moving emulsion under dispersing conditions with a washing fluid in at least two steps. Volume of washing fluid added in the first desalting step is larger than that in the second step by a factor of 2.0-2.5. Washing fluid is notably 3-10% aqueous sodium nitrate solution, which is preheated before addition to at least 45°C in both desalting steps. In the first step, oil is subjected to hot settling preferably for 2 h and, in the second step, 3 h. Demulsifier utilized is based on oil-soluble surfactants added in amounts 25 to 55 g/t.
EFFECT: reduced consumption of demulsifier at higher degree of desalting, in particular for oils with high level of chlorides.
7 cl, 2 ex
FIELD: petroleum extracting and petroleum processing industry.
SUBSTANCE: invention relates to preparing petroleum-soluble composite possessing high demulsifying effect. The composite is prepared by simple components mixing. As an active base the composite comprises sodium salt of oxyethylated isononylphenol carboxymethylate with the oxyethylation degree value 10-12. As a low-temperature solvent the composition comprises methanol-aldehyde fraction (waste in production of butyl alcohols) and water in the following ratio of components, wt.-%: oxyethylated isononylphenol carboxymethylate sodium salt, 45.0-55.0; methanol-aldehyde fraction, 43.5-50.0, and water, the balance, up to 100. Invention provides high demulsified capacity of the composition with low solidification point.
EFFECT: improved and valuable properties of composite.