Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G33/00—Dewatering or demulsification of hydrocarbon oils
  • C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means

Definitions

• the invention relates to a method for separating petroleum emulsions of the water-in-oil type using ester products.
• oil is diluted when oil is extracted.
• the water that is conveyed forms a water-in-oil emulsion with the oil.
• Salts such as sodium chloride, calcium chloride and / or magnesium chloride can be dissolved in the emulsified water.
• the emulsion water must be separated before the oil is transported to the refinery. In the refinery, before the distillation, the salt content is further reduced by renewed emulsion formation with fresh water and demulsification. A too high salt content in the crude oil could lead to malfunctions and corrosion in the refinery.
• a petroleum splitter also called a demulsifier or emulsion splitter, has the task of breaking the emulsion in as low a concentration as possible and, in this separation process, as far as possible without water or with minimal additional expenditure of heat and to achieve complete water separation and to reduce the salt content to a minimum.
• the quality criteria for delivered crude oil are the residual salt and the water content.
• the crude oils have different compositions depending on their provenance.
• the natural emulsion stabilizers have a complex, differentiated chemical Construction.
• selective splitters have to be developed.
• the different requirements for a petroleum splitter become even more diverse due to different production and processing conditions. Due to the constant opening up of new oil fields and the change in the production conditions of older oil fields, the development of optimal demulsifiers remains an acute problem, and a large number of different types of demulsifiers and demulsifier mixtures are required.
• esterification products are described as petroleum splitters in US Pat. No. 4,734,523 and in European Patent Application 0 333 135 A2 (Derwent unit, Accession Number 89-271925 / 38).
• the splitters in the US patent are reaction products of an oxyalkylated primary fatty amine and a diol compound with a dicarboxylic acid and those of the European patent application are reaction products of an oxyalkylated primary fatty amine and an adduct of a diol compound and a glycidyl ether with a dicarboxylic acid. With these demulsifiers a good and quick separation of water and salt is achieved.
• esterification products from an oxyalkylated primary fatty amine (as the sole component which supplies OH groups) and a dicarboxylic acid are also very effective petroleum splitters and that this is particularly the case when the esterification product consists of an oxyalkylated primary fatty amine and a dicarboxylic acid the group of dimeric (dimerized) fatty acids.
• the process according to the invention for separating petroleum emulsions of the water-in-oil type is accordingly characterized in that the emulsions are treated with an effective amount of an esterification product from an oxyalkylated primary fatty amine of the formula 1 below wherein R1 is an alkyl radical or alkenyl radical having 6 to 23 carbon atoms, R2 is H or CH3 and within the chain of the polyoxalkylene radical, arranged in blocks or randomly, can also take on both meanings, and a and b are numbers from a total of 2 to 30 , with the proviso that neither a nor b is zero, and 0.5 to 1.5 moles per mole of oxyalkylated primary fatty amine, preferably 0.5 to 1.1 moles per mole of oxyalkylated primary fatty amine, of a dicarboxylic acid, preferably one from the group of dimeric fatty acids.
• R1 is an alkyl radical or alkenyl radical having 6 to 23 carbon atom
• ester products would also be suitable as demulsifiers for any emulsion or even water-in-oil petroleum emulsions, and the preferred esterification products according to the invention (that is, those of an oxyalkylated primary fatty amine and a dimeric fatty acid as Dicarboxylic acid components) are not even mentioned in the two documents, they should rather be regarded as new.
• R 1 is a Is an alkyl radical with 8 to 18 carbon atoms or an alkenyl radical with 8 to 18 carbon atoms (it preferably contains 1 to 3 double bonds)
• R 2 is H and a and b (identical or different, whole or fractional) numbers from a total of 2 to 15, taking into account the stipulation given above.
• the oxyalkylation of primary fatty amines is well known and can be carried out by one of the methods for the oxyalkylation of compounds bearing acidic (active) H atoms.
• the oxyalkylated fatty amines can contain units of ethylene oxide or propylene oxide or units of ethylene oxide and propylene oxide which are present in random or block form in accordance with the meanings of R 2, preference being given to the ethoxylated primary fatty amines, ie those containing only ethylene oxide units.
• the fatty amines used for the oxyalkylation can, according to the meanings of R 1, be individual primary fatty amines or mixtures thereof.
• fatty amines whose hydrocarbon chain contains one or more double bonds, such as the residues of oleic, linoleic or linolenic acid.
• the preferred primary fatty amines are the technically available products such as stearylamine, coconut fatty amine or tallow fatty amine (in these technical products there are alkyl residues with essentially 8 to 18 carbon atoms).
• Preferred dicarboxylic acids are those of formula 2 below (these are simple dicarboxylic acids) HOOC-R3-COOH wherein R3 is an alkylene radical of the formula - (CH2) z -, in which z is an integer from 1 to 10, preferably 4 to 8, and wherein the alkylene radical with 1 or 2 OH groups or with 1 or 2 C1 to C18 -Alkyl or C3 to C18 alkenyl may be substituted, or is a vinylene radical or a p-phenylene radical, and those of formula 3 below (these are dicarboxylic acids from the group of dimerized unsaturated C18 fatty acids) HOOC-R4-COOH in which R4 is a divalent hydrocarbon radical with 34 C atoms (R4 thus represents the radical containing 34 C atoms which is formed during the dimerization of an unsaturated fatty acid with 18 C atoms to a dicarboxylic acid with a total of 36 C atoms).
• malonic acid succinic acid, glutaric acid, adipic acid, pimelic acid and so on may be mentioned in the homologous series, furthermore tartronic acid, malic acid and tartaric acid as well as fumaric acid and maleic acid and finally terephthalic acid.
• Particularly preferred simple dicarboxylic acids are those of the homologous series from adipic acid to sebacic acid, furthermore maleic acid, fumaric acid, dodecylsuccinic acid and dodecenylsuccinic acid. It goes without saying that instead of these dicarboxylic acids it is also possible to use their anhydrides, halides or esters of lower alkanols.
• Dimeric fatty acids are usually produced by addition polymerization (dimerization) of mono- or polyunsaturated fatty acids.
• the number of carbon atoms and the structure of the dicarboxylic acids obtained essentially depend on the starting fatty acids and on the reaction conditions during the dimerization.
• Various types and structures of dimeric fatty acids are commercially available.
• dimeric fatty acids preferred those which are produced by dimerization of unsaturated C18 fatty acids, for example oleic acid, linoleic acid, linolenic acid or tallow fatty acid (dimerization is known to mean the union of two identical molecules to form a new molecule, the dimer, by addition reaction).
• the dimerization of C18 fatty acids is usually carried out at a temperature of 150 to 250 ° C, preferably 180 to 230 ° C, with or without a dimerization catalyst.
• the dicarboxylic acid obtained (this is the dimeric fatty acid) corresponds to the formula 3 given, where R4 is the divalent link formed in the dimerization of the C18 fatty acid, which carries the two -COOH groups and has 34 carbon atoms.
• R4 is preferably an acyclic (aliphatic) or a mono- or bicyclic (cycloaliphatic) radical with 34 C atoms.
• the acyclic radical is usually a branched (substituted) and mono- to trisaturated alkyl radical with 34 carbon atoms.
• the cycloaliphatic radical generally also has 1 to 3 double bonds.
• the preferred dimeric fatty acids described are generally a mixture of two or more dicarboxylic acids of the formula 3 with structurally different R4 radicals.
• the dicarboxylic acid mixture often has a more or less large content of trimeric fatty acids which have arisen during the dimerization and have not been removed during the working up of the product by distillation.
• dimeric fatty acids which are formed in the dimerization of the C1, fatty acids mentioned are given in terms of formula, the hydrocarbon radical bearing the two -COOH groups being an acyclic, monocyclic or bicyclic radical:
• the dicarboxylic acids described ie the simple dicarboxylic acids and the dimeric fatty acids, the latter are preferred; they are generally technical products which are commercially available under the name "dimerized fatty acids” or "dimer fatty acids” and, as already mentioned above, can contain a more or less high proportion of trimerized fatty acids.
• the polycondensation esterification can be carried out using a higher-boiling inert solvent such as toluene, xylene or technical aromatic cuts or without solvent in the melt and under cover with a protective gas, preference being given to carrying out in solvents is.
• the reflux temperature of the reaction mixture is expediently chosen as the reaction temperature and the water of reaction formed is removed azeotropically.
• the water of reaction is distilled off directly from the reaction mixture.
• the reaction temperature is 100 to 220 ° C, preferably 130 to 200 ° C.
• an alkaline or acidic catalyst is used, as is expedient in esterification reactions, acidic catalysis with, for example, hydrohalic acid, phosphoric acid, sulfuric acid, sulfonic acid or haloacetic acid as the catalyst being preferred.
• acidic catalysis with, for example, hydrohalic acid, phosphoric acid, sulfuric acid, sulfonic acid or haloacetic acid as the catalyst being preferred.
• the course and the end of the reaction can be checked using the water of reaction formed or by determining the acid number. It is preferred to conduct the reaction to about 90 to 100% conversion, that is, until essentially no more water of reaction is formed.
• the procedure is preferably such that the two reaction components in the stated molar ratio, furthermore a solvent and acidic esterification catalyst are placed in a reaction vessel and this mixture is stirred at 100 to 220 ° C., preferably 130, while passing through an inert gas to 200 ° C, heated and held at this temperature with continuous discharge of the water formed (azeotropic distillation) until the reaction is complete.
• the esterification product obtained which generally has an acid number of ⁇ 10, preferably 2 to 8, can be purified from the catalyst used by washing with water and is the petroleum splitter according to the invention.
• the reaction time is in the range from 5 to 20 h.
• These esterification products are yellow to brown colored, more or less viscous liquids. They have a special chemical, especially when a dimerized fatty acid is used Structure on. Since their preparation is preferably carried out in the presence of solvents, they are generally in the form of a concentrated solution (active substance content preferably 60 to 80% by weight).
• the ester products (polyester) proposed according to the invention are notable for a high demulsifying effect.
• complete water separation and a reduction in salinity are achieved after a short separation time.
• raw oils that are specific to the consumption are obtained after a short separation time at the usual processing temperatures. They also have the effect that the separated water is practically free of oil, so that a complete oil separation from the separated water and thus good water quality is achieved.
• oil splitters a sharp separation between the oil and water phases is also achieved, which is another great advantage.
• the amount of demulsifier used according to the invention can vary within wide limits. It depends in particular on the type of petroleum and the processing temperature.
• the effective amount is generally 5 to 100 g per ton, preferably 10 to 50 g per ton.
• the splitters described are preferably used in solution for the purpose of better dosage and distributability.
• Water or organic liquids are suitable as solvents, for example alcohols such as methanol, isopropanol and / or butanol, aromatic hydrocarbons such as toluene and / or xylene or commercially available mixtures of higher aromatics.
• the two reaction components are therefore used in a molar ratio of 1: 1.
• 205 g of xylene are added as solvent, which is 25% by weight, based on the total weight of the two reaction components.
• the mixture is heated and kept at a temperature of 130 to 140 ° C for 2 hours, the reaction components reacting with esterification and the water of reaction distilled off azeotropically.
• the mixture is kept at a temperature of 160 to 170 ° C. for a further 10 hours.
• the course and the end of the esterification reaction are followed by determining the acid number.
• the esterification product obtained with a degree of conversion of 98% is a liquid with a viscosity of 1.1 Pa s.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Colloid Chemistry (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Treatment Of Liquids With Adsorbents In General (AREA)
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• 1992
  • 1992-05-30 DE DE4217985A patent/DE4217985A1/de not_active Withdrawn
• 1993
  • 1993-05-22 AT AT93108316T patent/ATE157116T1/de not_active IP Right Cessation
  • 1993-05-22 DE DE59307148T patent/DE59307148D1/de not_active Expired - Fee Related
  • 1993-05-22 DK DK93108316.6T patent/DK0572881T3/da active
  • 1993-05-22 EP EP93108316A patent/EP0572881B1/fr not_active Expired - Lifetime
  • 1993-05-27 US US08/068,630 patent/US5385674A/en not_active Expired - Lifetime
  • 1993-05-27 EG EG33493A patent/EG20364A/xx active
  • 1993-05-28 NO NO931718A patent/NO304797B1/no unknown
  • 1993-05-28 BR BR9302096A patent/BR9302096A/pt not_active IP Right Cessation
  • 1993-05-28 JP JP12755093A patent/JP3499900B2/ja not_active Expired - Fee Related
  • 1993-05-28 RU RU93005217A patent/RU2105788C1/ru active
  • 1993-05-28 MY MYPI93001019A patent/MY107782A/en unknown
  • 1993-05-28 MX MX9303169A patent/MX9303169A/es unknown

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