EP0175879B1 - Transport d'huiles brutes visqueuses - Google Patents

Transport d'huiles brutes visqueuses Download PDF

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Publication number
EP0175879B1
EP0175879B1 EP19850109481 EP85109481A EP0175879B1 EP 0175879 B1 EP0175879 B1 EP 0175879B1 EP 19850109481 EP19850109481 EP 19850109481 EP 85109481 A EP85109481 A EP 85109481A EP 0175879 B1 EP0175879 B1 EP 0175879B1
Authority
EP
European Patent Office
Prior art keywords
oil
water
emulsifier
degree
carboxymethylated
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
Application number
EP19850109481
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German (de)
English (en)
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EP0175879A2 (fr
EP0175879A3 (en
Inventor
Dieter Dr. Balzer
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Huels AG
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Huels AG
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Publication date
Application filed by Huels AG filed Critical Huels AG
Publication of EP0175879A2 publication Critical patent/EP0175879A2/fr
Publication of EP0175879A3 publication Critical patent/EP0175879A3/de
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Publication of EP0175879B1 publication Critical patent/EP0175879B1/fr
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17D—PIPE-LINE SYSTEMS; PIPE-LINES
    • F17D1/00—Pipe-line systems
    • F17D1/08—Pipe-line systems for liquids or viscous products
    • F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
    • 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
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/328—Oil emulsions containing water or any other hydrophilic phase
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T137/00—Fluid handling
    • Y10T137/0318—Processes
    • Y10T137/0391—Affecting flow by the addition of material or energy

Definitions

  • Heavy oils are difficult to transport in pipelines under conditions of usual outside temperatures due to their very high viscosity. To increase their mobility, they are therefore often mixed with low-viscosity crude oils or refinery cuts; such a procedure requires relatively high additives in order to achieve a noticeable improvement in flow. In addition, such a process is only possible where light oil fields exist at the same location or where a nearby refinery can supply low-viscosity gasoline fractions.
  • Another method also used is to add heat to the heavy oil in order to lower its viscosity and accordingly improve its fluidity, which requires considerable amounts of heat. So it is z. B. necessary to heat a heavy oil of 10.3 ° API, whose viscosity at 20 ° C is 40 000 mPa - s, to a temperature of approx. 95 ° C in order to achieve a viscosity of approx. 100 mPa ⁇ one for the oil transport in pipelines frequently required threshold value (ML Chirinos et al, Rev. Tec. Intevep 3 (2), 103 (1983). This means an extreme cost for the equipment and the supply of the pipelines and a loss of 15 to 20% Crude oil, since the necessary amount of heat is usually obtained by burning crude oil.
  • Another method of heavy oil transport consists in pumping the oil through the pipes in the form of a more or less easily liquid emulsion. Since the viscosity of emulsions is largely determined by that of the dispersing agent, this is an oil-in-water emulsion.
  • the oil-in-water emulsion is obtained by adding water and emulsifier to the oil using shear forces and then pumping this mixture into the pipeline.
  • a settling tank e.g. B. before entering the refinery, the emulsion is separated again in oil and water and the separated oil is fed to the refinery.
  • the lowest possible concentration of the emulsifier should lead to a stable, slightly liquid oil-in-water emulsion with a very high oil content, which naturally places high demands on the emulsifiers to be used.
  • High shear forces should also be avoided during emulsification, since there is a risk of inversion to a water-in-oil emulsion that is extremely highly viscous in heavy oils.
  • the emulsions are also said to be stable both to higher salinities such as occur in many deposit systems and to higher temperatures. Despite the stability of the emulsions as they flow through the pipeline, they should be able to be separated again without any problems. Sulfur-containing emulsifiers are undesirable if they fail to be kept in the aqueous phase during the cleavage.
  • carboxymethylated oxyethylates of the formula are used as emulsifiers in which R is a linear or branched aliphatic radical having 6 to 20 carbon atoms, an alkyl or dialkyl aromatic radical having 5 to 16 carbon atoms per alkyl group, n is 1 to 40 and M is an alkali metal or alkaline earth metal ion or ammonium.
  • the carboxymethylated oxyethylates according to DE-PS 24 18 444 are advantageously prepared by reacting oxethylates of the formula with chloroacetic acid or a salt of chloroacetic acid in the presence of alkali hydroxide or alkaline earth hydroxide.
  • R is preferably a saturated or unsaturated, straight-chain or branched alkyl radical having 8 to 18 carbon atoms or an alkylaryl radical having 5 to 16 carbon atoms in the alkyl group or a dialkyl radical having 3 to 16 carbon atoms per alkyl group.
  • alcohols whose oxethylates are carboxymethylated, z. B.
  • hexyl alcohol hexyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, isononyl alcohol, decyl and undecyl alcohol, lauryl, tridecyl, myristile, palmityl and stearyl alcohol, but also unsaturated, such as. B. oleyl alcohol.
  • alkylphenols e.g. B. Use: pentylphenol, hexylphenol, octylphenol, nonylphenol, dodecylphenol, hexadecylphenol and the corresponding dialkylphenols. Alkyl cresols and xylenols are also suitable.
  • the oxethylation can be carried out in the presence of catalytic amounts of alkali metal hydroxide, but it is known that other processes are also possible.
  • the degree of oxyethylation can assume values between 1 and 40, preferably between 3 and 20.
  • the cation in carboxymethylated oxethylate with the formula can be sodium, potassium, lithium, ammonium, calcium, magnesium or hydrogen.
  • the emulsifiers used are predominantly anionic, so that an unproblematic cleavage of the emulsion stabilized by them can be assumed.
  • the compounds are thermally stable and compatible with salt water within extremely wide limits (US Pat. No. 4,457,373). Furthermore, by varying the hydrophobic residue and the degree of oxyethylation, they allow the emulsifier to be optimally adapted to the oil to be transported and the given salinity of the water conveyed from the deposit in most cases, which advantageously forms the aqueous phase of the emulsion to be transported.
  • the carboxymethylated oxethylates can contain unreacted oxethylate. Accordingly, a degree of carboxymethylation can be defined.
  • the formula therefore denotes a mixture with different amounts of unreacted oxyethylate, provided that the degree of carboxymethylation is between 40 and 100%, preferably between 50 and 100%.
  • Mixtures with a degree of carboxymethylation between 85 and 100% are particularly effective. Such mixtures accordingly consist of anionic and nonionic surfactant and are considered as carboxymethylated oxethylates according to the invention.
  • mixtures of anionic and nonionic surfactant described or the purely anionic compounds (emulsifier) are soluble or at least easily dispersible in conventional reservoir waters.
  • the emulsifier to be used can be optimally adjusted to the existing heavy oil-water system according to its chemical structure.
  • the surfactants (emulsifiers) of a homologous series (cf.Table A) are dissolved in the water in question and mixed with the heavy oil in question and, after briefly stirring with a paddle stirrer without using high shear forces, they are tested for their emulsifying action and the stability of the emulsion is determined. This assessment of the emulsion is repeated about 24 hours later and then the viscosity is measured as a function of the shear rate, if necessary. Since heavy oil emulsions are somewhat structurally viscous, a range between 10 and 100 sec- 1 is selected for the shear rate, which corresponds approximately to the transport through pipelines. A surfactant is an optimal emulsifier if the amount necessary for emulsification is as small as possible.
  • the amount is generally from 0.01 to 0.5, in particular from 0.03 to 0.2,% by weight, based on the amount of oil, which corresponds to 100 to 5,000, preferably 300 to 2,000 ppm.
  • the emulsifier is metered in either as a melt or as an aqueous solution or as a dispersion of the oil-water mixture, or else it is added to the water, which is then mixed with the oil.
  • Water here is understood to mean either a more or less saline water that is produced together with the heavy oil, or it can be a cheaply available surface water or, finally, a mixture of both waters. Since heavy oil fields are often exploited by steam flooding, the salinity of the water produced can fluctuate somewhat, which is not critical for the claimed process.
  • the emulsifier can also be added to the heavy oil itself, especially since the surfactant class claimed here shows good oil solubility. It may be advantageous to use a small amount of a light hydrocarbon mixture as a solubilizer.
  • the mixing of the three components to form the emulsion, namely oil, water and emulsifier, can take place either directly at the borehole or in or near a collection tank or at any other point in the piping system.
  • the mixture ratio of oil to water can vary within wide limits between 10:90 and 90:10. For economic reasons, high oil contents should be aimed at, although it must be taken into account that very high oil contents usually also lead to relatively highly viscous oil-water emulsions.
  • the economic optimum is between 70 and 85% oil.
  • the emulsification is favored by mixing devices such as agitators, centrifugal pumps, static mixers, etc., which are used when necessary.
  • the emulsion formed in this way is conveyed through the pipeline system, which can contain intermediate stations and intermediate storage containers. At the pipeline end point, the emulsion is split in a separator, and it may be advantageous to add one or more desmulsifiers.
  • the crude oil dewatered in this way is drawn off and then either to the refinery or a possible further transport, e.g. B. supplied by ship.
  • the viscosity is measured, as already described.
  • the minimum emulsifier concentration (percent by weight, based on the amount of oil) of the surfactant in question is registered, which is necessary to produce an approximately stable emulsion. "Somewhat stable means that even slight stirring with the glass rod is sufficient to restore the original uniformity, if it has been lost at all.
  • the effectiveness of the surfactant can be optimized by varying the chemical structure (changing the degree of EO).
  • Carboxymethylated nonylphenoloxyethylates with an EO degree of approx. 3.3 have the highest effectiveness here.
  • the viscosity is approx. 100 mPa - s at 20 ° C - 100 mPa - s at 37.7 ° C are required - very low.
  • Table E shows the dependence of the emulsifying activity in the case of a carboxymethylated nonylphenol oxethylate on the degree of carboxymethylation.
  • the influence of alkaline earth ions is also examined. The effectiveness increases with increasing degree of carboxymethylation. This also applies in the presence of alkaline earth metal ions, which moreover weaken the emulsifying effect more than given additional alkaline halides in the same concentration given a high basic salinity.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Public Health (AREA)
  • Water Supply & Treatment (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Colloid Chemistry (AREA)

Claims (4)

1. Procédé pour le transport de pétrole brut visqueux par l'intermédiaire d'une canalisation, dans lequel on produit une émulsion huile-dans-l'eau, qui est constituée de pétrole brut et d'au moins 10 % d'eau contenant un émulsifiant et que l'on fait passer à travers la canalisation et que l'on sépare ensuite à nouveau en pétrole brut et en eau, caractérisé par le fait que l'on utilise, comme émulsifiant, un produit d'oxéthylation carboxyméthylé de formule
Figure imgb0014
dans laquelle R représente un radical aliphatique linéaire ou ramifié comportant de 6 à 20 atomes de carbone, un radical aromatique alkylé ou dialkylé comportant de 5 à 16 atomes de carbone par groupe alkyle, n représente un nombre d'une valeur de 1 à 40 et M représente un ion métallique alcalin ou alcalino-terreux, ou de l'ammonium.
2. Procédé selon la revendication 1, caractérisé par le fait que le taux de carboxyméthylation du produit d'oxéthylation carboxyméthylé est de 50 à 100 %.
3. Procédé selon la revendication 1, caractérisé par le fait que le taux de carboxyméthylation du produit d'oxéthylation carboxyméthylé est de 85 à 100 %.
4. Procédé selon les revendications 1 à 3, caractérisé par le fait que la concentration d'émulsifiant, relativement à la quantité de pétrole, est de 0,01 à 0,5 % en poids (100 à 5000 ppm).
EP19850109481 1984-09-27 1985-07-27 Transport d'huiles brutes visqueuses Expired EP0175879B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843435430 DE3435430A1 (de) 1984-09-27 1984-09-27 Verfahren zum transport von zaehfluessigen rohoelen
DE3435430 1984-09-27

Publications (3)

Publication Number Publication Date
EP0175879A2 EP0175879A2 (fr) 1986-04-02
EP0175879A3 EP0175879A3 (en) 1987-02-04
EP0175879B1 true EP0175879B1 (fr) 1989-02-22

Family

ID=6246476

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19850109481 Expired EP0175879B1 (fr) 1984-09-27 1985-07-27 Transport d'huiles brutes visqueuses

Country Status (4)

Country Link
US (1) US4736764A (fr)
EP (1) EP0175879B1 (fr)
CA (1) CA1242952A (fr)
DE (2) DE3435430A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3607090A1 (de) * 1986-03-05 1987-09-10 Huels Chemische Werke Ag Verfahren zum transport von schweroelen
DE3609641A1 (de) * 1986-03-21 1987-09-24 Huels Chemische Werke Ag Verfahren zum transport von zaehfluessigen oelen
US4978365A (en) * 1986-11-24 1990-12-18 Canadian Occidental Petroleum Ltd. Preparation of improved stable crude oil transport emulsions
NO864988D0 (no) * 1986-12-10 1986-12-10 Dyno Industrier As Oppgradering av tunge voksholdige oljefraksjoner til bruk som lette fyringsoljer eller dieseloljer samt oppgraderte oljer.
US5354504A (en) * 1991-08-19 1994-10-11 Intevep, S.A. Method of preparation of emulsions of viscous hydrocarbon in water which inhibits aging
EP0606443A1 (fr) * 1992-08-05 1994-07-20 Kao Corporation Combustible a base d'emulsion d'huile super-lourde et procede permettant de regenerer un combustible degrade a base d'emulsion aqueuse d'huile super-lourde
US7450993B2 (en) * 2004-09-08 2008-11-11 Spinal Modulation, Inc. Methods for selective stimulation of a ganglion

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2183853A (en) * 1934-12-22 1939-12-19 Ig Farbenindustrie Ag Polyoxyalkylene ether acid compounds containing a higher aliphatic group
US3519006A (en) * 1966-12-05 1970-07-07 Ralph Simon Pipelining oil/water mixtures
US3491835A (en) * 1967-12-29 1970-01-27 Phillips Petroleum Co Recovering,desalting,and transporting heavy crude oils
US3467195A (en) * 1968-04-25 1969-09-16 Chevron Res Pumping viscous crude
US4249554A (en) * 1979-01-26 1981-02-10 Conoco, Inc. Method of transporting viscous hydrocarbons
CA1117568A (fr) * 1979-04-19 1982-02-02 Thomas R. Sifferman Methode de transport d'hydrocarbures visqueux
US4265264A (en) * 1979-04-30 1981-05-05 Conoco, Inc. Method of transporting viscous hydrocarbons
US4285356A (en) * 1979-10-12 1981-08-25 Conoco, Inc. Method of transporting viscous hydrocarbons
EP0047370B1 (fr) * 1980-09-10 1983-08-17 Hüls Aktiengesellschaft Procédé pour la récupération de pétrole d'une formation souterraine
DE3105913C2 (de) * 1981-02-18 1983-10-27 Chemische Werke Hüls AG, 4370 Marl Verfahren zur Gewinnung von Öl aus unterirdischen Lagerstätten durch Emulsionsfluten
ATE17772T1 (de) * 1981-09-01 1986-02-15 Huels Chemische Werke Ag Verfahren zur gewinnung von oel aus einer unterirdischen lagerstaette.

Also Published As

Publication number Publication date
EP0175879A2 (fr) 1986-04-02
DE3568346D1 (en) 1989-03-30
DE3435430A1 (de) 1986-04-03
EP0175879A3 (en) 1987-02-04
CA1242952A (fr) 1988-10-11
US4736764A (en) 1988-04-12

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