EP0584708B1 - Désémulsifiants polyfonctionnels pour huiles brutes - Google Patents

Désémulsifiants polyfonctionnels pour huiles brutes Download PDF

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Publication number
EP0584708B1
EP0584708B1 EP93113206A EP93113206A EP0584708B1 EP 0584708 B1 EP0584708 B1 EP 0584708B1 EP 93113206 A EP93113206 A EP 93113206A EP 93113206 A EP93113206 A EP 93113206A EP 0584708 B1 EP0584708 B1 EP 0584708B1
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EP
European Patent Office
Prior art keywords
formula
mol
ethylene oxide
stage
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP93113206A
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German (de)
English (en)
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EP0584708A1 (fr
Inventor
Martin Dr. Hille
Rainer Dr. Kupfer
Roland Böhm
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Clariant Produkte Deutschland GmbH
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Clariant GmbH
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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) where R is C 6 -C 22 alkyl, preferably C 8 -C 18 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 an oxyalkylated precursor of the formula (I), in which z is 0, as demulsifiers, corrosion inhibitors and / or pour point depressants.
  • 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 of 100-150 ° C, preferably 130-140 ° C.
  • the amount of wagered The catalyst / base 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 Mol of starting amine corresponds to the values given for x and y and den specified weight percentages for z.
  • the amine of the formula (II), (III), (IV) and / or (V) initially charged 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 the range from 100 to 150.degree. C., preferably in the range from 130 to 140.degree. C., the desired amount of propylene oxide usually being 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 thus prepared (I) can be reacted with additional ethylene oxide in a further stage will.
  • the amount added is in the range from 0 to 70% by weight Ethylene oxide, based on an oxyalkylated precursor of the formula (I), in which z is 0.
  • This additional addition of ethylene oxide after the one already done Propoxylation is carried out analogously to the reaction with propylene oxide, with one additional alkalization can be dispensed with.
  • the compounds of the formula (I) are used as additives for crude oils, being used both as demulsifiers, corrosion inhibitors and Lower pour point.
  • the iodine color number means the concentration of free iodine in an iodine-iodine-potassium solution (in mg iodine per 100 ml iodine-iodine-potassium solution) and is used for Identification of the color or translucency of this solution and similar liquids.
  • the basis for determining the iodine color number is Iodine color scale (comparison tube).
  • the content of the autoclave is now 3.2 g of a 40% aqueous KOH solution added and the water at 80 ° C within 2 h in a water jet vacuum away.
  • Ethylene oxide (EO) (166.3 g, 3.78 mol) metered in to the extent that it reacts.
  • the pressure in the Autoclaves to 3-4 bar, the reaction temperature is between 130 and 140 ° C (reaction time 8 h).
  • the mixture is still Post-reaction for 2 h at 130 ° C, whereupon the pressure at 1 bar constant remains and indicates the end of the reaction.
  • 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 yellow, clear liquid; it has an alkali number of 32.5 mg KOH / g substance and a cloud point of 37.9 ° C (according to DIN 53917).
  • 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 (after DIN 53917).
  • Torpedo glasses are characterized by the fact that they are strong downwards taper and have a scaling, creating small volumes separated water can be read well.
  • Torpedo glasses filled with crude oil emulsions are made using a micro-dosing syringe each added a defined amount of demulsifier.
  • the Separated amounts of water are expressed in milliliters (ml) or in percent (%), based on the total amount of water in the crude oil emulsion, specified.
  • the total amount of water present in the crude oil emulsion must as well as the dosing amount of demulsifier and the optimal The gap temperature can 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 amount of emulsion of 100 cm 3 is used in the experiments; 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.
  • 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 cm 2 of steel 1.1203 are dynamically aged in a mixture of salt water (5% by weight NaCl) and petroleum (9: 1) at 70 ° C for 24 hours, the pH value the aqueous phase is adjusted 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. example Amount used in ppm 5 10th 50 1 54 80 86 2nd 66 84 90 3rd 70 82 88 4th 68 83 87 5 48 78 83 6 52 80 84

Landscapes

  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (2)

  1. Utilisation d'amines grasses alcoxylées et de dérivés d'amines grasses de formule générale (I) : où A est un reste de formule (II) à (V) avec R égal à un groupe alkyle en C6-C22, de préférence alkyle en C8-C18,
    x est un nombre de 5 à 40, de préférence de 8 à 20,
    y est un nombre de 5 à 70, de préférence de 10 à 30, et
    z est égal à 0 à 70 % en poids, de préférence de 0 à 40 % en poids d'oxyde d'éthylène par rapport à un précurseur alcoxylé de formule (I) où z vaut 0, comme agents désémulsionnants, comme inhibiteurs de corrosion et/ou agents d'abaissement du point de figeage.
  2. Utilisation selon la revendication 1, caractérisée en ce que l'on ajoute les amines grasses et les dérivés d'amines grasses alcoxylés de formule (I) dans une quantité de 2 à 2000 ppm au pétrole brut.
EP93113206A 1992-08-22 1993-08-18 Désémulsifiants polyfonctionnels pour huiles brutes Expired - Lifetime EP0584708B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4227911 1992-08-22
DE4227911 1992-08-22

Publications (2)

Publication Number Publication Date
EP0584708A1 EP0584708A1 (fr) 1994-03-02
EP0584708B1 true EP0584708B1 (fr) 1998-05-13

Family

ID=6466190

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93113206A Expired - Lifetime EP0584708B1 (fr) 1992-08-22 1993-08-18 Désémulsifiants polyfonctionnels pour huiles brutes

Country Status (8)

Country Link
US (1) US5421993A (fr)
EP (1) EP0584708B1 (fr)
BR (1) BR9303442A (fr)
CA (1) CA2104506C (fr)
DE (1) DE59308532D1 (fr)
MX (1) MX9305090A (fr)
NO (1) NO305485B1 (fr)
RU (1) RU2122563C1 (fr)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19642493A1 (de) * 1996-10-15 1998-04-16 Clariant Gmbh Verwendung von Alkansulfonsäuren als Asphalten-Dispergatoren
DE19642494A1 (de) * 1996-10-15 1998-04-16 Clariant Gmbh Verwendung von Sarkosinaten als Asphalten-Dispergatoren
DE19643832A1 (de) 1996-10-30 1998-05-07 Clariant Gmbh Schwere Öle mit verbesserten Eigenschaften und ein Additiv dafür
DE19709797A1 (de) 1997-03-10 1998-09-17 Clariant Gmbh Synergistische Mischungen von Alkylphenolformaldehydharzen mit oxalkylierten Aminen als Asphalten-Dispergatoren
US6103100A (en) * 1998-07-01 2000-08-15 Betzdearborn Inc. Methods for inhibiting corrosion
EP1091085A1 (fr) * 1999-10-09 2001-04-11 Cognis Deutschland GmbH, Dep. Intellectual Properties Inhibiteurs d Asphaltères
US7247606B2 (en) * 2001-11-05 2007-07-24 Cognis Corporation Branched reaction products
US7745501B2 (en) * 2006-06-22 2010-06-29 Momentive Performance Materials Inc. Method for demulsifying
MY153421A (en) * 2007-06-20 2015-02-13 Akzo Nobel Nv A method for preventing the formation of calcium carboxylate deposits in the dewatering process for crude oil/water streams
US8030363B2 (en) 2008-01-25 2011-10-04 Momentive Performance Materials Inc. Polyorganosiloxane demulsifier compositions and methods of making the same
MX2008015756A (es) * 2008-12-10 2010-06-10 Mexicano Inst Petrol Formulaciones desemulsificantes y deshidratantes para crudos pesados a base de copolimeros en bloques bifuncionalizados con aminas.
CN103193971B (zh) * 2013-04-16 2015-08-26 西南石油大学 以二氢化牛油基仲胺为起始剂的聚环氧丙烷油头及嵌段聚醚破乳剂及其制备方法
CN103755884B (zh) * 2013-12-20 2016-03-30 西南石油大学 一种处理油田聚驱采出液用反相破乳剂及其制备方法
RU2558359C1 (ru) * 2014-07-23 2015-08-10 Открытое Акционерное Общество "Научно-исследовательский институт по нефтепромысловой химии" (ОАО "НИИнефтепромхим") Депрессорная присадка для парафинистых нефтей и предотвращения асфальтено-смоло-парафиновых отложений
CN105368428B (zh) * 2014-08-27 2019-12-10 中国石油化工股份有限公司 阴非混合型驱油表面活性剂及其制备方法和用途
CN106590595B (zh) * 2015-10-20 2020-02-07 中国石油化工股份有限公司 适用于低钙镁油藏驱油组合物及其制备方法
RU2627355C1 (ru) * 2016-11-15 2017-08-07 Общество с ограниченной ответственностью "МИРРИКО" Противотурбулентная присадка с антикоррозионными свойствами
US10557099B2 (en) * 2017-08-09 2020-02-11 General Electric Company Oil based product for treating vanadium rich oils
US10577553B2 (en) 2017-08-09 2020-03-03 General Electric Company Water based product for treating vanadium rich oils
WO2019236779A1 (fr) * 2018-06-08 2019-12-12 Huntsman Petrochemical Llc Polyesters d'amine d'alkyle alcoxylés utilisés comme abaisseurs de point d'écoulement destinés à des carburants
CA3225519A1 (fr) 2021-07-16 2023-01-19 Innospec Limited Compositions de mazout et procedes et utilisations associes
CN114250082B (zh) * 2021-12-03 2023-03-07 浙江皇马科技股份有限公司 一种原油破乳剂的制备方法
WO2024073492A1 (fr) 2022-09-28 2024-04-04 Championx Llc Composition d'inhibiteur d'asphaltène à libération prolongée

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1166400B (de) * 1959-02-26 1964-03-26 Hoechst Ag Verfahren zum Spalten von Erdoelemulsionen
DE3635235A1 (de) * 1986-10-16 1988-05-05 Basf Ag Alkoxylierte amidgruppenhaltige polyamide und deren verwendung zum brechen von oel-in-wasser- und wasser -in-oel-emulsionen
DE3638743A1 (de) * 1986-11-13 1988-05-26 Hoechst Ag Verzweigte polyoxalkylenmischpolyester, verfahren zu ihrer herstellung und ihre verwendung
DE3809067A1 (de) * 1988-03-18 1989-09-28 Hoechst Ag Verfahren zum trennen von erdoelemulsionen vom typ wasser-in-oel
DE4020664A1 (de) * 1990-06-29 1992-01-02 Basf Ag Ester enthaltende kraftstoffe fuer ottomotoren und dieselmotoren

Also Published As

Publication number Publication date
NO305485B1 (no) 1999-06-07
CA2104506A1 (fr) 1994-02-23
MX9305090A (es) 1994-06-30
NO932975D0 (no) 1993-08-20
EP0584708A1 (fr) 1994-03-02
CA2104506C (fr) 2004-11-23
NO932975L (no) 1994-02-23
DE59308532D1 (de) 1998-06-18
US5421993A (en) 1995-06-06
RU2122563C1 (ru) 1998-11-27
BR9303442A (pt) 1994-03-15

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