Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
• • 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 extracted crude oil usually contains a number of disruptive accompanying substances, such as water, inorganic salts and paraffins and asphaltenes, which are usually removed before transport or storage.
• Water-in-oil emulsions often cause corrosion and microbiological growth in the water-wetted parts of the pipes and tank systems.
• demulsifiers By using suitable demulsifiers, the water-in-oil emulsions are split and thus the water and salt content of the crude oil is reduced.
• the crude oils contain large amounts of paraffins and asphaltenes, they have a high pour point, which in some cases leads to deposits in the production probes and especially in the pipelines and can bring the production and pumping of the crude oil to a standstill.
• US-A-2 557 081 describes the use of oxyalkylated alkylphenol formaldehyde resins as demulsifiers. From US-A-2 674 619 and US-A-2 677 700 the use of polyalkylene oxide block polymers as demulsifiers is known. US-A-3 974 220 describes the use of alkyldiamine salts and alkylammonium compounds as demulsifiers with a corrosion-inhibiting effect.
• EP-A-186 009 discloses the use of oxyethylated amines, also in combination with ethylene copolymers, as pour point depressants.
• the invention relates to the use of oxyalkylated fatty amines and fatty amine derivatives of the general formula (I) in which A is a radical of the formula (II) - (V) with R equal to C6-C22-alkyl, preferably C8-C18-alkyl x is a number from 5 to 40, preferably 8 to 20, y is a number from 5 to 70, preferably 10 to 30, and z is 0 to 70% by weight, preferably 0 to 40% by weight, based on compounds of the formula (I) with x ethylene oxide units and y propylene oxide units, as demulsifiers, corrosion inhibitors and / or pour point depressants.
• A is a radical of the formula (II) - (V) with R equal to C6-C22-alkyl, preferably C8-C18-alkyl x is a number from 5 to 40, preferably 8 to 20, y is a number from 5 to 70, preferably 10 to 30, and z
• the free valences of the nitrogen atoms of the radicals of the formulas (II) to (V) contain radicals of the general formula (I) without A.
• the compounds of the formula (I) are prepared by reacting amines of the formulas (II) to (V) with ethylene oxide and propylene oxide with the addition of bases, such as alkali metal hydroxides.
• the reaction takes place in several stages at temperatures in the range from 100 to 150 ° C., preferably 130 to 140 ° C.
• the amount of catalyst / base used is usually 0.5 to 3.0% by weight, based on the starting amine used.
• the molar amount of ethylene oxide and propylene oxide per mole of starting amine corresponds to the values given for x and y and the weight percentages given for z.
• the amine of the formula (II), (III), (IV) and / or (V) which is initially introduced is heated to a temperature of approximately 130 to 140 ° C. and initially reacted with 1 mole of ethylene oxide per equivalent of NH function, whereupon the alkali metal hydroxide is added as a powder or in the form of an aqueous solution.
• an aqueous, preferably 40% by weight aqueous solution it is necessary to remove the water present before adding the remaining amounts of ethylene oxide. This is done in a simple and gentle way by applying a vacuum.
• the alkalized oxethylate obtained is then also reacted at 130 ° C. with the desired residual amount of ethylene oxide.
• the reaction mixture is kept at a temperature of approximately 130 to 140 ° C. for the after-reaction for several hours.
• the end of the reaction is indicated by constant pressure at approximately one bar. It has been shown that because of the exothermic reaction, it is advantageous to add said residual amount of ethylene oxide in several stages. This can be achieved by gradual addition in small amounts or continuous addition.
• the reaction temperature is in the range of 130 to 140 ° C and the pressure is approximately 3-4 bar. Depending on the amount of ethylene oxide, the addition takes several hours, on average 6-8 hours.
• the reaction mixture is kept at a temperature of 130 to 140 ° C. for several hours, preferably 2 hours. The end of the reaction is indicated by constant pressure at approximately one bar.
• the finished oxethylate obtained is reacted with propylene oxide in a further stage.
• This propylene oxide is added at a temperature in Range of 100 to 150 ° C, preferably in the range of 130 - 140 ° C, with the desired amount of propylene oxide is usually added to the extent that its reaction takes place.
• the pressure in the reaction vessel rises to approximately 3-4 bar.
• the reaction mixture is kept at a temperature in the range from approximately 130 to 140 ° C. until the end of the reaction is indicated by constant pressure in the range of one bar.
• the ethoxylated and propoxylated compounds of the formula (I) thus prepared can be reacted with additional ethylene oxide in a further step.
• the amount added is in the range from 0 to 70% by weight of ethylene oxide, based on compounds of the formula (I) with x ethylene oxide units and y propylene oxide units.
• This additional addition of ethylene oxide after the propoxylation has already taken place is carried out analogously to the reaction with propylene oxide, it being possible to dispense with an additional alkalization.
• the compounds of the formula (I) are used as additives for crude oils, and they act both as demulsifiers, corrosion inhibitors and lower pour points.
• characterization such as alkali number and iodine color number, are determined or determined as follows:
• the iodine color number means the concentration of free iodine in an iodine-iodide-potassium solution (in mg iodine per 100 ml of iodine-iodine-potassium solution) and serves to identify the color or translucency of this solution and similar liquids.
• the basis for the determination of the iodine color number is the iodine color scale (comparison tube).
• the contents of the autoclave are then mixed with 3.2 g of a 40% aqueous KOH solution and the water is removed at 80 ° C. in the course of 2 hours in a water jet vacuum.
• Ethylene oxide (EO) (166.3 g, 3.78 mol) is metered into the alkalized fatty amine oxyethylate to the extent that it reacts.
• the pressure in the autoclave rises to 3-4 bar, the reaction temperature is between 130 and 140 ° C (reaction time 8 h).
• reaction time 8 h reaction time 8 h
• propylene oxide (PO) (364 g, 6.27 mol) is now metered into the above product to the extent that it reacts.
• the pressure rises to a maximum of 3 bar, the temperature to a maximum of 130 ° C.
• the addition is complete after about 10 h; the after-reaction takes place at 130 ° C. for 2 h, whereupon the pressure remains constant at 1 bar and indicates the end of the reaction.
• the product thus obtained is a light yellow, pasty mass with an alkali number of 22.5 mg KOH / g substance and a cloud point of 44.1 ° C (according to DIN 53917). All cloud points were determined with a 5 g weight (product) on 25 g of a 25% aqueous butyl diglycol solution.
• the product is produced analogously to Example 1.
• the product is produced analogously to Example 1.
• the product is produced analogously to Example 1.
• the product is a light brown, slightly cloudy liquid with an alkali number of 18.8 mg KOH / g substance and a cloud point of 52.2 ° C (according to DIN 53917).
• the product is a light brown, slightly cloudy liquid; it has an alkali number of 20.4 mg KOH / g substance and a cloud point of 42.7 ° C (according to DIN 53917).
• Torpedo glasses are characterized by the fact that they taper down sharply and have a scale, which means that small volumes of separated water can be easily read.
• a defined amount of demulsifier is added to each of the torpedo glasses filled with the crude oil emulsions using a micro-dosing syringe.
• the torpedo glasses filled with crude oil emulsion and demulsifier are placed in a tempered water bath and the separated amounts of water are read at constant intervals.
• the amounts of water separated are given in milliliters (ml) or in percent (%), based on the total amount of water present in the crude oil emulsion.
• the total amount of water present in the crude oil emulsion as well as the metered amount of demulsifier and the optimal cracking temperature must be determined before the demulsification test.
• the crude oil emulsion of northern German origin used in the tests has a water content of approx. 68% and a salt content of approx. 18%.
• an emulsion amount of 100 cm3 is used; the dewatering temperature is 50 ° C.
• the amount (concentration) of demulsifier used in Examples 1 to 6 is 30 ppm each.
• Table I shows the characteristics of the compounds of formula I. example Compounds of formula I. A R x [EO] y [PO] e.g.
• the amount of water separated after 30, 60, 90, 180, 240 and 300 minutes is given in% of the total water (Table 2).
• Table 2 The amount of water separated after 30, 60, 90, 180, 240 and 300 minutes is given in% of the total water (Table 2).
• example Time / minutes 30th 60 90 180 240 300 1 2nd 14 32 66 88 92 2nd 1 4th 12th 28 42 72 3rd 8th 26 74 96 98 100 4th 12th 36 80 96 98 100 5 20th 48 84 98 100 100 6 16 35 72 86 96 98
• the test is carried out according to the Shell Wheel test. Coupons with a surface area of 15 cm2 made of steel 1.1203 are dynamically aged in a mixture of salt water (5% by weight NaCl) and petroleum (9: 1) for 24 hours at 70 ° C, the pH of the aqueous Phase is set to 3.5 with acetic acid. The coupons are then cleaned and the weight loss determined.
• This test is a standard test for oil field corrosion inhibitors.
• Table 3 lists the protection values in% of the compounds of the formula (I).
• the protection value is the reduction of the removal, ie the corrosion compared to the coupons without inhibitor in the liquid mixture.

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• Chemical & Material Sciences (AREA)
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• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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• 1993
  • 1993-08-18 EP EP93113206A patent/EP0584708B1/fr not_active Expired - Lifetime
  • 1993-08-18 DE DE59308532T patent/DE59308532D1/de not_active Expired - Fee Related
  • 1993-08-19 US US08/109,335 patent/US5421993A/en not_active Expired - Fee Related
  • 1993-08-20 CA CA002104506A patent/CA2104506C/fr not_active Expired - Fee Related
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  • 1993-08-20 RU RU93043258A patent/RU2122563C1/ru active
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