EP0531807B1 - Procédé de stockage et de transport d'hydrocarbures liquides - Google Patents

Procédé de stockage et de transport d'hydrocarbures liquides Download PDF

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Publication number
EP0531807B1
EP0531807B1 EP19920114585 EP92114585A EP0531807B1 EP 0531807 B1 EP0531807 B1 EP 0531807B1 EP 19920114585 EP19920114585 EP 19920114585 EP 92114585 A EP92114585 A EP 92114585A EP 0531807 B1 EP0531807 B1 EP 0531807B1
Authority
EP
European Patent Office
Prior art keywords
hydrocarbon
gel
surfactant
rich
weight
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
EP19920114585
Other languages
German (de)
English (en)
Other versions
EP0531807A1 (fr
Inventor
Fritz Dr. Engelhardt
Gerlinde Dr. Ebert
Heinz Prof. Dr. Hoffmann
Gerhard Prof. Dr. Platz
Werner Dr. Ritschel
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.)
Sanofi Aventis Deutschland GmbH
Cassella Farbwerke Mainkur AG
Original Assignee
Cassella AG
Cassella Farbwerke Mainkur AG
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 Cassella AG, Cassella Farbwerke Mainkur AG filed Critical Cassella AG
Publication of EP0531807A1 publication Critical patent/EP0531807A1/fr
Application granted granted Critical
Publication of EP0531807B1 publication Critical patent/EP0531807B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C10L7/00—Fuels produced by solidifying fluid fuels
    • 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
    • Y10T137/0324—With control of flow by a condition or characteristic of a fluid
    • Y10T137/0329—Mixing of plural fluids of diverse characteristics or conditions
    • 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
    • Y10T137/0324—With control of flow by a condition or characteristic of a fluid
    • Y10T137/0329—Mixing of plural fluids of diverse characteristics or conditions
    • Y10T137/0335—Controlled by consistency of mixture
    • 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

  • the present invention relates to a method for the safe storage or transport of liquid hydrocarbons, the hydrocarbon being converted into a hydrocarbon-rich gel which is destroyed again after storage or transport, and a method for destroying a hydrocarbon-rich gel.
  • the object of the present invention is therefore to provide a method for the safe storage or transport of hydrocarbons.
  • hydrocarbons are stored or transported in the form of hydrocarbon-rich gels.
  • a hydrocarbon-rich gel is understood to mean a system consisting of polyhedra formed by surfactant and filled with hydrocarbon, water forming a continuous phase in the narrow spaces between the polyhedra. Systems of this type are known and in Angew. Chem. 100 933 (1988) and Ber. Bunsenges. Phys. Chem. 92 1158 (1988).
  • Hydrocarbon-rich gels are characterized by the appearance of a yield point. This flow limit is reached when the gel no longer withstands the stress (shear, deformation) and begins to flow. Below the yield point, the gel structures have solid properties and obey Hooke's law. Ideally, the system is equivalent to a Newtonian liquid above the yield point. This means that hydrocarbon-rich gels can be pumped in a simple manner, but cannot flow at rest due to their solid-state properties. This means that they cannot escape from defective storage or transport containers, and there is almost no risk to the environment.
  • the present invention relates to a method for the safe storage or transport of liquid hydrocarbons, which is described in claim 1.
  • the present invention further relates to a method described in claim 2 for destroying a hydrocarbon-rich gel.
  • Surfactant and water are preferably added to the hydrocarbon in amounts such that a hydrocarbon-rich gel is formed from 70 to 99.5% by weight of hydrocarbon, 0.01 to 15% by weight of surfactant and 0.49 to 15% by weight of water.
  • Surfactant and water are particularly preferably added to the hydrocarbon in amounts such that a hydrocarbon-rich gel is formed from 80 to 99.5% by weight of hydrocarbon, 0.01 to 5% by weight of surfactant and 0.49 to 15% by weight of water.
  • Hydrocarbons which are particularly suitable for the process according to the invention are n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane, n-tetradecane, n-hexadecane, cyclohexane, Cyclooctane, benzene, toluene, kerosene, gasoline, unleaded gasoline, heating oil, diesel oil and crude oil.
  • Anionic, cationic, amphoteric or nonionic surfactants can be used to form the hydrocarbon-rich gels.
  • Preferred cationic surfactants are Quaternary ammonium compounds of the formula wherein R1 alkyl with 10 to 22 carbon atoms, R2 alkyl with 1 to 12 carbon atoms or benzyl R3 and R4 independently of one another hydrogen or methyl and X ⁇ Cl ⁇ , Br ⁇ or CH3SO4 ⁇ ; Fatty amines, such as, for example, coconut fatty amines, lauryl fatty amine, oleyl fatty amine, stearyl fatty amine, tallow fatty amine, dimethyl fatty amines or chain-pure primary alkyl amines having 8 to 22 carbon atoms; Ammonium borate betaine based on didecylamine; Stearyl-N-acylamido-N-methyl-imidazolinium chloride of the formula Alkenyl succinic acid derivatives of the formulas where R is iso-C18H35 or polybutenyl.
  • Mechanical waves are understood to mean, in particular, pressure waves of high frequency, for example ultrasound.
  • pressure waves of high frequency for example ultrasound.
  • the preferred range is of course dependent on the boiling point of the hydrocarbon.
  • a vacuum of up to 0.1 torr is usually advantageous.
  • oppositely charged surfactants or polymers or copolymers are preferably used.
  • the above-mentioned anionic surfactants are particularly preferably used.
  • Particularly preferred polymers with anionic groups are, for example
  • Polyacrylates consisting of basic elements of the formula which can also be networked and / or completely or partially neutralized
  • Poly-2-acrylamido-2-methyl-propanesulfonic acids consisting of basic elements of the formula which can also be networked and / or completely or partially neutralized
  • polyvinylphosphonic acids consisting of basic elements of the formula which can also be networked and / or completely or partially neutralized.
  • Cross-linked, partially neutralized polyacrylic acid is very particularly preferred. This also has the advantage that, due to its enormous absorption capacity for water, it can bind the aqueous phase of the gel to be destroyed quantitatively. Because of this absorption capacity for water, crosslinked, partially neutralized polyacrylic acid can not only destroy gel structures based on cationic surfactants, but also those based on anionic, amphoteric or nonionic surfactants.
  • the above-mentioned cationic surfactants are particularly preferably used.
  • Particularly preferred polymers with cationic groups are, for example Poly-diallyl-dimethyl-ammonium chloride, which can also be cross-linked and / or completely or partially neutralized, or poly-methacrylic acid-2-dimethylaminoethyl ester consisting of basic elements of the formula which can also be networked and / or completely or partially neutralized.
  • the destruction of the gel structure is carried out in a simple manner so that the surfactant or polymer as such or in a suitable solvent is added to the gel structure and briefly shaken.
  • the gel disintegrates spontaneously and is faster the higher the counter ion concentration.
  • Suitable solvents in which the surfactant or polymer used for gel destruction can be dissolved are, for example, xylene, water or alcohols.
  • the concentrations of the surfactants in the solvents are not critical, but are preferably from 30% by weight until the solution is saturated. If the hydrocarbon to be stored or transported is a fuel or lubricating oil, it is particularly advantageous if surfactants which can remain as an additive in the hydrocarbon are selected both for gel formation and for gel destruction.
  • surfactants which can remain as an additive in the hydrocarbon are selected both for gel formation and for gel destruction.
  • sulfonates are known as detergent additives
  • alkenylsuccinic acid imidoamines are known as dispersant additives (J. Raddatz, WS Bartz, 5th International Coll. January 14-16, 1986, Esslingen Technical Academy "Additives for Lubricants and Working Fluids").
  • Succinimides are also known as oil and fuel additives (see, for example, EP 198 690, US 4,614,603, EP 119 675, DE 3 814 601 or EP 295 789).
  • the pumping power proves to be independent of the pumping speed due to the viscoelasticity of the gel systems.
  • Example 1a 50 g of the gel prepared according to Example 1a were connected to an oil pump in a 1 liter one-necked flask via vacuum regulator and cold trap. At a vacuum of 0.6 mm Hg, the gel disintegration started within 5 minutes when the flask was heated by means of a thermostat bath to a gel temperature of 30 to 40 ° C. and was over after a short time.
  • a hydrocarbon-rich gel of 1.6 g of sodium dodecyl sulfate, 6.4 g of H2O and 392 g of kerosene was prepared as described in Example 1a, the mixing being carried out using a Vortex Genie mixer.
  • the gel decomposition was carried out analogously to Examples 1d to 1g.
  • a hydrocarbon-rich gel made from 1.6 g of a commercially available nonionic surfactant based on a nonylphenol polyglycol ether, 6.4 g H2O and 392 g kerosene was prepared as described in Example 1a.
  • a hydrocarbon-rich gel of 1.6 g of sodium dodeyl sulfate, 6.4 g of H2O and 392 g of hexane was prepared as described in Example 1a.
  • a hydrocarbon-rich gel from 1.6 g of a commercial cationic surfactant based on a quaternary ammonium compound, 6.4 g H2O and 392 g kerosene was prepared as described in Example 1a.
  • hydrocarbon-rich gels of Examples 6 to 19 below were prepared from ligroin, anionic surfactant and water and 41 g each were destroyed with the stated amount of cationic surfactant.
  • the following cationic surfactants were used:
  • hydrocarbon-rich gels of Examples 20 to 36 below were prepared from ligroin, cationic surfactant and water and 1 g each was destroyed with the stated amount of anionic surfactant.
  • hydrocarbon-rich gels of Examples 37 to 50 below were prepared from ligroin, surfactant and water and 1 g each was destroyed with the stated amount of an oppositely charged polymer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Colloid Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (6)

  1. Procédé pour le stockage sans risque, respectivement pour le transport sans risque, d'hydrocarbures liquides par
    a) transformation de l'hydrocarbure en un gel riche en hydrocarbures par addition d'un agent tensio-actif et d'eau et
    b) destruction du gel riche en hydrocarbures après stockage, respectivement transport, effectué,
    caractérisé en ce qu'on détruit le gel riche en hydrocarbures par traitement avec des ondes mécaniques, par application d'une pression réduite, respectivement du vide ou, si le gel riche en hydrocarbures est formé à l'aide d'un agent tensio-actif ionique, par addition de polymères, respectivement de copolymères, ou d'agents tensio-actifs de charge opposée.
  2. Procédé pour la destruction d'un gel riche en hydrocarbures par traitement avec des ondes mécaniques, par application d'une pression réduite, respectivement du vide, ou si le gel est formé à l'aide d'un agent tensio-actif ionique, par addition de polymères, respectivement de copolymères, ou d'agents tensio-actifs de charge opposée.
  3. Procédé selon la revendication 1 et/ou 2, caractérisé en ce que le gel riche en hydrocarbures se compose de 70 à 99,5 % en poids d'hydrocarbures, de 0,01 à 15% en poids d'agent tensio-actif et de 0,49 à 15% en poids d'eau.
  4. Procédé selon une ou plusieurs des revendications 1 à 3, caractérisé en ce que le gel riche en hydrocarbures se compose de 80 à 99,5% en poids d'hydrocarbures, de 0,01 à 5% en poids d'agent tensio-actif et de 0,49 à 15% en poids d'eau.
  5. Procédé selon une ou plusieurs des revendications 1 à 4, caractérisé en ce qu'on utilise en tant qu'hydrocarbures les n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-décane, n-dodécane, n-tétradécane, n-hexadécane, cyclohexane, cyclooctane, benzène, toluène, kérosène, essence, essence sans plomb, fioule de chauffage, carburant diesel ou pétrole brut.
  6. Procédé selon une ou plusieurs des revendications 1 à 5, caractérisé en ce qu'on utilise en tant qu'agents tensio-actifs des agents tensio-actifs anioniques, cationiques, amphotères ou non ioniques.
EP19920114585 1991-09-09 1992-08-27 Procédé de stockage et de transport d'hydrocarbures liquides Expired - Lifetime EP0531807B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4129943A DE4129943A1 (de) 1991-09-09 1991-09-09 Verfahren zur lagerung bzw. zum transport von fluessigen kohlenwasserstoffen
DE4129943 1991-09-09

Publications (2)

Publication Number Publication Date
EP0531807A1 EP0531807A1 (fr) 1993-03-17
EP0531807B1 true EP0531807B1 (fr) 1995-03-15

Family

ID=6440200

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19920114585 Expired - Lifetime EP0531807B1 (fr) 1991-09-09 1992-08-27 Procédé de stockage et de transport d'hydrocarbures liquides

Country Status (6)

Country Link
US (1) US5276248A (fr)
EP (1) EP0531807B1 (fr)
JP (1) JPH07179870A (fr)
AT (1) ATE119934T1 (fr)
CA (1) CA2077705A1 (fr)
DE (2) DE4129943A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2150055C1 (ru) * 1995-04-18 2000-05-27 Эдвансед Молекулар Текнолоджиз, Л.Л.С. Способ нагревания жидкости и устройство для его осуществления
US6019499A (en) * 1995-04-18 2000-02-01 Advanced Molecular Technologies, Llc Method of conditioning hydrocarbon liquids and an apparatus for carrying out the method
US6194622B1 (en) * 1998-06-10 2001-02-27 Exxonmobil Upstream Research Company Method for inhibiting hydrate formation
US6222083B1 (en) 1999-10-01 2001-04-24 Exxonmobil Upstream Research Company Method for inhibiting hydrate formation
US6584781B2 (en) 2000-09-05 2003-07-01 Enersea Transport, Llc Methods and apparatus for compressed gas
US6994104B2 (en) * 2000-09-05 2006-02-07 Enersea Transport, Llc Modular system for storing gas cylinders
US7405188B2 (en) 2001-12-12 2008-07-29 Wsp Chemicals & Technology, Llc Polymeric gel system and compositions for treating keratin substrates containing same
US8273693B2 (en) * 2001-12-12 2012-09-25 Clearwater International Llc Polymeric gel system and methods for making and using same in hydrocarbon recovery
US7183239B2 (en) * 2001-12-12 2007-02-27 Clearwater International, Llc Gel plugs and pigs for pipeline use
US8099997B2 (en) 2007-06-22 2012-01-24 Weatherford/Lamb, Inc. Potassium formate gel designed for the prevention of water ingress and dewatering of pipelines or flowlines
US8065905B2 (en) 2007-06-22 2011-11-29 Clearwater International, Llc Composition and method for pipeline conditioning and freezing point suppression
US20130025857A1 (en) * 2011-07-27 2013-01-31 Conlen Surfactant Technology, Inc. Preserving oil gravity

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2890257A (en) * 1955-12-28 1959-06-09 Pure Oil Co Method of stabilizing odorless naphthas during storage
US3378418A (en) * 1966-04-11 1968-04-16 Petrolite Corp Method of resolving thixotropic jet and rocket fuel emulsions
US3416320A (en) * 1967-07-14 1968-12-17 Exxon Research Engineering Co Turbo-jet propulsion method using emulsified fuels and demulsification

Also Published As

Publication number Publication date
US5276248A (en) 1994-01-04
DE4129943A1 (de) 1993-03-11
EP0531807A1 (fr) 1993-03-17
CA2077705A1 (fr) 1993-03-10
DE59201653D1 (de) 1995-04-20
ATE119934T1 (de) 1995-04-15
JPH07179870A (ja) 1995-07-18

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