EP0763077A1 - Procede permettant de separer l'eau du petrole brut et agent de craquage d'emulsion d'huile brute utilise a cet effet - Google Patents

Procede permettant de separer l'eau du petrole brut et agent de craquage d'emulsion d'huile brute utilise a cet effet

Info

Publication number
EP0763077A1
EP0763077A1 EP95920064A EP95920064A EP0763077A1 EP 0763077 A1 EP0763077 A1 EP 0763077A1 EP 95920064 A EP95920064 A EP 95920064A EP 95920064 A EP95920064 A EP 95920064A EP 0763077 A1 EP0763077 A1 EP 0763077A1
Authority
EP
European Patent Office
Prior art keywords
group
alkoxylates
alkoxylated
compounds
mono
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.)
Withdrawn
Application number
EP95920064A
Other languages
German (de)
English (en)
Inventor
Wolfgang Knauf
Knut Oppenländer
Wilhemus Slotman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Baker Hughes Ltd
Original Assignee
BASF SE
Baker Hughes Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE, Baker Hughes Ltd filed Critical BASF SE
Publication of EP0763077A1 publication Critical patent/EP0763077A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B01D17/047—Breaking emulsions with separation aids
    • 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 present invention relates to an improved method for separating water from crude oil.
  • the invention further relates to the petroleum emulsion splitters used here.
  • the Rohole differ greatly in their composition depending on their provenance.
  • the natural emulsifiers contained in the crude oils also have a complicated chemical structure, so that selective petroleum emulsion splitters (demulsifiers) have to be developed to overcome their effect.
  • the development of new crude oil fields as well as changed funding requirements for older fields mean that new demulsifiers are constantly required, which result in faster separation into water and oil and as little residual water and residual salt as possible.
  • EP-A 549 918 discloses petroleum emulsion splitters based on an alkoxylate, for example monohydric or dihydric alcohols reacted with 3 to 100 mol ethylene oxide, propylene oxide or butylene oxide per hydroxyl group, such as ethylene glycol, diethylene glycol or butylene glycol.
  • alkoxylate for example monohydric or dihydric alcohols reacted with 3 to 100 mol ethylene oxide, propylene oxide or butylene oxide per hydroxyl group, such as ethylene glycol, diethylene glycol or butylene glycol.
  • cleavage-active alcohol alkoxylates can also be used together with oxalkylated polyalkylene polyamines, which are also emulsion-cleavage-active.
  • the present invention was therefore based on the object of providing petroleum emulsion splitters which, in the shortest possible time, allow the emulsion to be separated as quantitatively as possible into water and water, i.e. which show good effectiveness even in low doses.
  • condensation products from mono- or oligoamine alkoxylates, dicarboxylic acids and alkylene oxide block copolymers these condensation products also being able to be completely or partially quaternized on the nitrogen atoms, or
  • R 1 is a single group to ten divalent radical of a C ⁇ ⁇ to C 2 o alkyl group, a phenyl group or an Al ylphenyl distr having 1 to 20 carbon atoms in the alkyl group referred to,
  • a 1 to A 3 each have a 1,2-alkylene group with 2 to
  • n stands for a number from 1 to 10
  • a denotes a number from 1 to 50
  • b c and d each stand for numbers from 0 to 50
  • the sum of b + c + d is greater than 3
  • Substances of the following structure types known as petroleum emulsion breakers are preferably used as cleavage-active compounds A.
  • a 1 has the meaning given above, k is a number from 1 to 200, preferably 5 to 150, in particular 10 to 100, and x is a number from 10 to 2 500, preferably 40 to 1 200;
  • R2 straight-chain or branched - to C 3 o-alkyl, straight-chain or branched C 2 - to C3o-alkenyl or
  • Phenylalkyl designated with 1 to 20 carbon atoms in the alkyl group
  • R 3 for a grouping of the formula - (XO) . —H is or has the meaning of R 2 ,
  • X is one or different in block form
  • 1,2-alkylene groups having 2 to 4 carbon atoms having 2 to 4 carbon atoms, k has the meaning given above and m represents a number from 1 to 10, preferably 1 to 4;
  • R 4 denotes a straight-chain or branched Ci to C 2 o -alkyl radical, in particular C - to -CC alkyl radical, p stands for a number from 1 to 75, preferably 2 to 40, and
  • R 5 represents hydrogen, Ci to C alkyl or benzyl, q denotes a number from 1 to 100, preferably 3 to 50, and R 4 , X and k have the meanings given above; (e) copolymers and terpolymers of alkoxylated acrylic or methacrylic esters of the general formula VIII
  • R 6 represents hydrogen or methyl
  • R 6 has the meaning given above, R 7 is hydrogen or the radical —COOH, —COOC 2 H 4 OH,
  • R8 denotes hydrogen or the radical —COOH
  • R 9 is a straight-chain or branched Ci to -C alkylene group, Y is one or different in block form
  • condensation products X can also be completely or partially quaternized on the nitrogen atoms by, for example, C 1 -C 4 -alkyl groups or benzyl radicals;
  • Mixtures of the cleavage-active compounds A mentioned can also be used, for example mixtures of the substances of the structure types (a) + (c), (a) + (d), (a) + (e), (a) + (f) , (b) + (c), (b) + (e) or (b) + (f).
  • the groupings A 1 , A 2 , A 3 or X and Y are based on
  • 1, 2-alkylene oxides such as butylene oxide, but especially ethylene oxide and propylene oxide, or on styrene oxide.
  • Suitable straight-chain or branched monovalent alkyl radicals R 1 , R 2 , R 4 and R 5 which are addressed as Ci to C 4 , Ci to C 0 or Ci to C 3 o-alkyl radicals, are, for example, suitable Methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, tert-pentyl, neo-pentyl, n-hexyl , n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, iso-tridecyl, n-t
  • Examples of multi-bonded alkyl radicals R 1 include ⁇ , ⁇ -alkylene radicals, glycerol radicals, the rest of pentaerythritol or the like
  • radical R 4 in particular C 1 -C 2 -alkyl radicals such as tert-butyl, n-pentyl, n-octyl, n-nonyl, iso-nonyl or n-dodecyl are suitable.
  • Suitable straight-chain or branched C 2 - to C 3 o-alkenyl radicals R 2 are, for example, vinyl, allyl, methallyl, oleyl, linolyl or linolenyl.
  • Alkylphenyl groups with 1 to 20 carbon atoms in the alkyl radical for R 1 are, for example, groupings of the formula
  • Phenylalkyl groups with 1 to 20 carbon atoms in the alkyl group are, for example, benzyl, 2-phenylethyl, 3-phenylpropyl or 4-phenylbutyl.
  • Examples of compounds V are correspondingly alkoxylated ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylene pentamine.
  • Polymer splitters of the structure type (s) are described in EP-A 264 841. Specific examples of such connections are given there.
  • the non-cleavage-active polyalkylene glycol ethers I used as demulsifying agents are alkoxylation products based on mono-, di- or polyhydric alcohols or phenols.
  • the value of the alcohol or phenol n is preferably 1 to 5, in particular 1 to 3, especially 1 or 2.
  • the degree of alkoxylation a in the compounds I is preferably 2 to 15, in particular 3 to 10, especially at 4 to 7.
  • Examples of compounds I are ethylene glycol or propylene glycol reacted with 2, 3, 4, 5, 6, 7, 8, 9 or 10 mol ethylene oxide or propylene oxide, n-propanol reacted with 1, 2, 3, 4 or 5 mol ethylene oxide or propylene oxide , n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol or 2-ethylhexanol, with 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 mol of ethylene oxide or propylene oxide reacted glycerol and phenol reacted with 1, 2, 3, 4, 5, 6 or 7 mol of ethylene oxide or propylene oxide, p-tert-butylphenol, p-pentylphenol, p-octylphenol, p-nonylphenol, p- iso-nonylphenol or p-dodecylphenol.
  • the non-cleavage-active block copolymers II used as demulsifying aids have total degrees of alkoxylation b + c + d of 4 to 150, in particular 7 to 100, especially of
  • Block copolymers II from a single block for example ethylene oxide or propylene oxide, from two blocks, for example ethylene oxide + propylene oxide, can be used , or from three blocks, for example ethylene oxide + propylene oxide + ethylene oxide or propylene oxide + ethylene oxide + propylene oxide.
  • the demulsifying agents I and in particular II used can be amphiphilic in nature, ie with a more hydrophilic end and a more hydrophobic other end, for example ethylene oxide / propylene oxide block copolymers, or non-amphiphilic in nature, for example pure ethylene oxide or pure propylene oxide block copolymers.
  • the demulsifying agents B used according to the invention are to be classified as (practically) non-emulsion-splitting active and thus differ from the structure of the alkoxylates active in emulsion splitting mentioned in the prior art, for example in EP-A 549 918.
  • the demulsifying agents I and II do not cause water to be separated from crude oil, as is also demonstrated by the experimental examples listed below.
  • the described demulsifying agents B can generally be used in related technical fields together with an actual emulsion splitter for better and faster splitting of water-in-oil emulsions.
  • Components A and B are preferably used in the separation process according to the invention of water from crude oil in a weight ratio of 98: 2 to 30:70, in particular 95: 5 to 40:60, especially 90:10 to 50:50.
  • the optimal ratio depends on the chemical structure of compounds A and B, but also on the crude oil used.
  • the spectrum of action runs through a maximum that has a specific position for each system. If B is overdosed, this substance then only acts as a diluent and the emulsion-splitting effect of the mixture of A and B decreases, based on the total amount of the mixture.
  • the present invention also relates to a petroleum emulsion-splitting mixture of
  • R 1 denotes a mono- to ten-bonded radical of a C 1 -C 2 o -alkyl group, a phenyl group or an al ylphenyl group • with 1 to 20 C atoms in the alkyl radical,
  • a 1 to A 3 each a 1,2-alkylene group with 2 to
  • n stands for a number from 1 to 10
  • a denotes a number from 1 to 50
  • b c and d each stand for numbers from 0 to 50
  • the sum of b + c + d is greater than 3
  • splitter mixtures described are expediently added to the crude oil emulsions in amounts of 1 to 1000 ppm, preferably 5 to
  • the splitter mixtures can also be used as solutions because of their better meterability.
  • Mixtures of organic solvents for example methanol
  • organic solvents with boiling limits between 50 and 200 ° C. alone can serve as solvents, for example toluene, xylenes, tetrahydrofuran, dioxane, lower alcohols and light petrol fractions of the boiling point mentioned. If solutions are used, these are expediently adjusted to an active substance content (content of splitter mixture) of 0.5 to 50% by weight.
  • the solutions are preferably added to the crude oils at the probes (in the field).
  • the cleavage then takes place at the temperature of the freshly required water-in-oil emulsion at such a speed that the emulsion can be broken on the way to the processing plant. There it is separated in a possibly heated separator and possibly with the aid of an electrical field into pure oil and salt water (formation water) without difficulty.
  • Demulsifying agent (B1) commercial propylene oxide-ethylene oxide block copolymer with a
  • Raw emulsion Northern German I (water content; approx. 45% by weight)
  • Emulsion splitter (AI) as in Table 1
  • Emulsion splitter (AI! As in Table 1
  • Demulsifying agent (B2) commercial propylene oxide
  • Raw emulsion Northern German I (water content: approx. 45% by weight)
  • Emulsion splitter (AI) as in Table 1
  • Amount of mixtures of AI and B2 added 100 ppm each Mixtures of separated amount of formation water [ml] Al B2 20 30 45 60 2 h 4 h 16 h [wt .-%] [wt .-%] min min min min
  • Emulsion splitter (AI! As in Table 1
  • Demulsifying agent (B3) with 5 mol propylene oxide at 120 to

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé qui permet de séparer l'eau du pétrole brut, grâce à l'utilisation comme agent de craquage d'émulsion d'huile brute, d'un mélange comprenant: A) des composés à effet de craquage de structure-type des: (a) polyéthylènimine-alcoxylates, (b) mono- ou oligoamine-alcoxylates, (c) résines alkylphénol-formaldéhyde alcoxylées, (d) résines alkylphénol-formaldéhyde modifiées par amine alcoxylées, (e) co- ou terpolymérisats d'esters d'acide acrylique ou méthacryliques alcoxylés avec des composés vinyle, (f) produits de condensation issus de mono- ou d'oligoamine-alcoxylates, d'acides dicarboxyliques et de polymères séquencés d'oxyde d'alkylène, ces produits de condensation pouvant également être entièrement ou partiellement quaternisés au niveau des atomes d'azote ou (g) composés (a) à (f) mis à réagir avec des réticulants, et B) comme auxiliaires de désémulsification, des éthers polyalkylèneglycol n'ayant pas d'effet de craquage, des formules générales (I): R1[(OA1)a—OH]n ou (II): H—(OA1)b—(OA2)c—(OA3)d—OH dans lesquelles R1 désigne un reste ayant entre 1 et 10 liaisons d'un groupe alkyle C¿1?-C20, d'un groupe phényle ou d'un groupe alkylphényle ayant entre 1 et 20 atomes de C dans le reste alkyle, A?1 à A3¿ désigne chacun un groupe 1,2-alkylène ayant entre 2 et 4 atomes de C ou un groupe phényléthylène, n vaut entre 1 et 10, a vaut entre 1 et 50 et b, c et d valent chacun entre 0 et 50, la somme de b + c + d étant supérieure à 3.
EP95920064A 1994-05-30 1995-05-19 Procede permettant de separer l'eau du petrole brut et agent de craquage d'emulsion d'huile brute utilise a cet effet Withdrawn EP0763077A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4418800A DE4418800A1 (de) 1994-05-30 1994-05-30 Verfahren zur Abtrennung vom Wasser aus Rohöl und hierbei verwendete Erdölemulsionsspalter
DE4418800 1994-05-30
PCT/EP1995/001901 WO1995033018A1 (fr) 1994-05-30 1995-05-19 Procede permettant de separer l'eau du petrole brut et agent de craquage d'emulsion d'huile brute utilise a cet effet

Publications (1)

Publication Number Publication Date
EP0763077A1 true EP0763077A1 (fr) 1997-03-19

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP95920064A Withdrawn EP0763077A1 (fr) 1994-05-30 1995-05-19 Procede permettant de separer l'eau du petrole brut et agent de craquage d'emulsion d'huile brute utilise a cet effet

Country Status (5)

Country Link
US (1) US5759409A (fr)
EP (1) EP0763077A1 (fr)
DE (1) DE4418800A1 (fr)
NO (1) NO965114L (fr)
WO (1) WO1995033018A1 (fr)

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Also Published As

Publication number Publication date
NO965114D0 (no) 1996-11-29
NO965114L (no) 1996-12-02
WO1995033018A1 (fr) 1995-12-07
US5759409A (en) 1998-06-02
DE4418800A1 (de) 1995-12-07

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