EP3615638B1 - Verfahren zur odorierung von kryogenen flüssigkeiten - Google Patents

Verfahren zur odorierung von kryogenen flüssigkeiten Download PDF

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EP3615638B1
EP3615638B1 EP18722690.7A EP18722690A EP3615638B1 EP 3615638 B1 EP3615638 B1 EP 3615638B1 EP 18722690 A EP18722690 A EP 18722690A EP 3615638 B1 EP3615638 B1 EP 3615638B1
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Prior art keywords
cryogenic fluid
odorizing agent
odorizing
agent
temperature
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French (fr)
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EP3615638A1 (de
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Jean-Benoît CAZAUX
Laurent BARBON
Patrick Charles
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Arkema France SA
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Arkema France SA
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    • 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
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/003—Additives for gaseous fuels
    • C10L3/006—Additives for gaseous fuels detectable by the senses
    • 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
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • 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
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/08—Inhibitors
    • C10L2230/081—Anti-oxidants
    • 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
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/08—Inhibitors
    • C10L2230/088—Inhibitors for inhibiting or avoiding odor
    • 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
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/50—Screws or pistons for moving along solids

Definitions

  • the present invention relates to a process for odorizing cryogenic fluid, in particular in order to allow its olfactory detection and to alert of possible leaks, in particular when the cryogenic fluid may represent a danger by inhalation, a risk of explosion, and others.
  • the present invention also relates to a device making it possible to odorize the cryogenic fluid by applying the method of the invention.
  • odorizing gases are now well known, and in particular techniques for odorizing natural gas, as described for example in EP1758970 , EP1934314 and EP2038382 .
  • an odorizing formulation liquid at ambient temperature, is added to a fuel in the gas state, for example natural gas.
  • cryogenic fluid within the meaning of the present invention, is meant any fluid which can be stored in the liquid state under cryogenic conditions, that is to say at temperatures of the order of -150° C. and below -150°C.
  • cryogenic fluids are, by way of non-limiting example, light alkanes (methane, ethane, propane), C 2 -C 5 alkenes, inert gases (for example nitrogen), industrial gases (oxygen, hydrogen ), and others.
  • odorizing agent odorization
  • odorization of a cryogenic fluid requires the dissolution of a generally very small and controlled quantity of the odorizing principle in said cryogenic fluid, so that the odorant is present homogeneously in the cryogenic fluid and that when vapors of said cryogenic fluid (for example in the event of a leak, when it is at ambient temperature) an effective quantity of odorant is definitely present in said vapors and that the olfactory detection threshold in the air is reached to allow the alert required.
  • the document DE102004050419 describes a process for odorizing a liquid cryogenic fuel, the odorization operation being carried out on the fluid in the gaseous state, after evaporation of said cryogenic fluid.
  • the diluent used must comply with imperative conditions in terms of crystallization point, with respect to the odorizer and with respect to the natural gas to be odorized, so that the diluent mainly mentioned, if not only mentioned, is propane.
  • propane propane
  • Another disadvantage linked to the aforementioned technique is the pollution of the fluid to be odorized by the appropriate diluent, (propane), which can be annoying, depending on the nature of the cryogenic fluid to be odorized and the use that is made of it subsequently. .
  • the aim of the present invention is to propose a process that is simple to implement, particularly on an industrial level, that is to say for the odorization of very large quantities of cryogenic fluids, without having the known drawbacks of the techniques of the prior art, in particular those implementing a diluent that can pollute said cryogenic fluid to be odorized, and thus potentially be a nuisance for the use made of said cryogenic fluid.
  • Another object of the invention is to provide a process that is simple to implement, particularly industrially, while allowing a controlled addition without restrictions with regard to the conditions of flow rates and pressure of an odorizing agent to be introduced.
  • each of steps a), b) and c) of the process is carried out continuously.
  • the flow rate of odorizing agent in the contact zone is proportional to the flow rate of the cryogenic fluid.
  • the flow rate of odorizing agent in the contact zone is slaved to the flow rate of the cryogenic fluid.
  • the amount of odorizing agent coming into contact with the cryogenic fluid to be odorized is between the minimum amount necessary to odorize said cryogenic fluid and the maximum to reach saturation. Too large an amount of odorizing agent in the cryogenic fluid can lead to solid deposits which could damage or even clog pipes, valves, and other components present on the industrial site for odorizing said cryogenic fluid.
  • Step b) of supplying the buffer zone makes it possible to isolate the supply zone from the contact zone which is at the temperature of the cryogenic fluid.
  • the odorizing agent (optionally in the form of an odorizing formulation) is, and remains, in the liquid state in the feed zone and is gradually brought to a temperature below 30°C above the temperature of the cryogenic fluid, or even the temperature of the cryogenic fluid, on leaving this buffer zone.
  • the odorizing agent in step b), is brought to a temperature below 20° C., preferably below 10° C. above the temperature of the cryogenic fluid to be odorized.
  • step c) the odorizing agent cooled in step b) is brought into contact with said cryogenic fluid to be odorized.
  • the odorizing agent is most often in solid form, advantageously in the form of droplets of solidified odorizing agent or else in the form of a solidified spray.
  • step c) the odorizing agent comes into contact with the cryogenic fluid and is entrained with the flow of cryogenic fluid, in which it dissolves, thus allowing the odorization of said cryogenic fluid.
  • the odorizing agent is dispersed/mixed with the cryogenic fluid.
  • This dispersion or mixing can be carried out according to any method known to those skilled in the art, for example by simple contact of the odorizing agent with a flow of cryogenic fluid, or even by means of any mechanical means, such as a static mixer, agitator, propeller, and others.
  • the mixture is produced by simple contact of the odorizing agent with a flow of cryogenic fluid in a turbulent regime.
  • turbulent regime we mean a flow defined by a Reynolds number greater than the critical Reynolds number, that is to say, for a flow in a tubular pipe, a Reynolds number greater than 2000, or even greater than 3000.
  • the supply of odorizing agent is such that the concentration of odorizing agent in the cryogenic fluid is between 0.1 mg/m 3 (n) and 500 mg/m 3 (n), preferably between 0. 5 mg/m 3 (n) and 100 mg/m 3 (n), more preferably between 0.5 mg/m 3 (n) and 50 mg/m 3 (n).
  • the concentration is measured relative to m 3 (n) corresponding to 1 m 3 of gas in the vapor state under normal temperature and pressure conditions (0°C and 1013.25 hPa).
  • the odorizing agent implemented in the present invention can be of any kind, depending on the desired effect, the desired detection threshold, the expected odor, and others.
  • the odorizing agent is advantageously chosen from the family of hydrocarbons, for example terpenes, from the family of alcohols and phenols, from the family of aldehydes, from the family of ethers, cyclic or not, from the family of esters, by for example the family of acrylates and (alkyl)acrylates, in the family of fatty acids, in the family of ketones, in the family of lactones, in the family of mercaptans, for example alkylmercaptans, (alkyl)thio-alkylmercaptans, the family of cyclic sulphides, the family of symmetrical or unsymmetrical dialkyl sulphides, the family of symmetrical or unsymmetrical dialkyl disulphides, or else in the family of selenium derivatives, for example selenides or diselenides of alkyl or dialkyl, that whether they are symmetrical or not.
  • Mixtures of at least two of the odorizing agents mentioned above, in all proportions, can
  • the odorizing agent is chosen from alcohols and phenols, such as, for example and without limitation, nerol, phenyl-3-propan-1-ol, linalool, geosmin, p-cresol, 3,5-dimethylphenol, 3-ethylphenol and 1-naphthol.
  • alcohols and phenols such as, for example and without limitation, nerol, phenyl-3-propan-1-ol, linalool, geosmin, p-cresol, 3,5-dimethylphenol, 3-ethylphenol and 1-naphthol.
  • the odorizing agent is chosen from the family of aldehydes, such as, for example and without limitation, trans-2,trans-4-decadienal, trans-2,trans-4-hexadienal, trans-2,trans-4-octadienal, trans-2,trans-4-nonadienal, ethyl vanillin, cis-3-hexenal, trans-4-hexenal, trans-2,cis-6-nonadienal , 4,5-epoxy-2-dodecenal and iso -valeraldehyde.
  • aldehydes such as, for example and without limitation, trans-2,trans-4-decadienal, trans-2,trans-4-hexadienal, trans-2,trans-4-octadienal, trans-2,trans-4-nonadienal, ethyl vanillin, cis-3-hexenal, trans-4-hexenal, trans-2,cis-6-nonadien
  • the odorizing agent is chosen from the family of ethers, such as, without limitation, 1-methoxynaphthalene, 2-methoxynaphthalene, 1-ethoxynaphthalene, pyrans, for example cis -rose-oxide.
  • the odorizing agent is chosen from the family of mercaptans, such as, without limitation, methyl mercaptan, ethyl mercaptan, tert-butyl mercaptan, sec-butyl mercaptan, iso - butyl mercaptan, n-propyl mercaptan, iso -propyl mercaptan, pentyl mercaptans, cyclohexyl mercaptan, and n-dodecyl mercaptan.
  • family of mercaptans such as, without limitation, methyl mercaptan, ethyl mercaptan, tert-butyl mercaptan, sec-butyl mercaptan, iso - butyl mercaptan, n-propyl mercaptan, iso -propyl mercaptan, pentyl mercaptans, cyclohex
  • the odorizing agent is chosen from the family of alkyl sulphides, disulphides or even polysulphides, such as, without limitation, methyl and ethyl sulphide (MES), sulphide (DMS) and diethyl sulfide (DES) or tetrahydrothiophene (THT).
  • MES methyl and ethyl sulphide
  • DMS sulphide
  • DES diethyl sulfide
  • TTT tetrahydrothiophene
  • the odorizing agent is chosen from the family of esters, such as, without limitation, methyl, ethyl, allyl, n-propyl, iso -propyl, n-butyl, iso -butyl, tert -butyl, pentyl, hexyl, heptyl, octyl and dodecyl, methyl, ethyl, allyl methacrylates, n-propyl, iso -propyl, n-butyl, iso -butyl, tert -butyl, pentyl, hexyl, heptyl, octyl and dodecyl, iso -valerate propyl, iso -pentyl iso -valerate, methyl dodecanoate, ethyl dodecanoate, ethyl undecanoate, methylhepty
  • the odorizing agent is chosen from the family of fatty acids such as, but not limited to, butyric acid, iso-valeric acid and methyl-2-propionic acid.
  • the odorizing agent is chosen from the family of nitrogen compounds comprising, by way of non-limiting examples, lactones (such as caprolactone), nitriles (such as 2-nonenenitrile) and pyrazine compounds (such as 2-methylpyrazine, 2,3-dimethylpyrazine, 2,6-dimethylpyrazine, 2,3,5-trimethylpyrazine, tetramethylpyrazine, 2-ethylpyrazine, 2,3- diethylpyrazine, 5,2-methylethylpyrazine, 2,3-methylethylpyrazine, 5,2,3-methyldiethylpyrazine and 3,5,2- as well as 3,6,2-dimethylethylpyrazine), 2,3-methylethylpyrazine and tetramethylpyrazine, and others, as mentioned in document DE19837066 .
  • lactones such as caprolactone
  • nitriles such as 2-nonenen
  • ketones also represents a family of preferred odorizing agents, ketones among which mention may be made, by way of nonlimiting examples, of 3-methylnonan-2,4-dione, 1-nonen-3-one, 3-hydroxy-4,5-dimethyl-2(5 H )-furanone, 3-hydroxy-4,5-diethyl-2(5 H )-furanone, 3-hydroxy-4-methyl-5-ethyl- 2(5 H )-furanone, 3-hydroxy-4-ethyl-5-methyl-2(5 H )-furanone, 3-hydroxy-4-methyl-5-butyl-2(5 H )-furanone, 3-hydroxy-4-methyl-5- iso -butyl-2( 5H )-furanone, 3-hydroxy-4-methyl-5-propyl-2( 5H )-furanone, 2,5-dimethyl -4-methoxy-3(2 H )-furanone, ionones, damascenones, trans-2-nonen-4-one, furan
  • lactones such as, for example, and in a non-limiting manner, 3,6-dimethyl-3a,4,5,7a-tetrahydro-2( 3H )-benzofuranone, ⁇ -nonalactone, ⁇ -undecalactone, (Z)-6-dodeceno- ⁇ -lactone, and coumarin.
  • the odorizing agent is chosen from the family of selenium derivatives, among which mention may be made, by way of non-limiting examples, of dimethyl selenide, dimethyl diselenide, diethyl selenide , diphenyl selenide, diphenyl diselenide and ethylselenol, and others, such as those mentioned in the document WO2015050509 .
  • the perception thresholds for the odorants cited above are all of the order of the order of magnitude of ten parts per billion (ppb), or even lower. They are mostly below 1 ppb.
  • the odorizing agent which can be used in the present invention is chosen from methyl and ethyl sulphide, dimethyl sulphide, diethyl sulphide, dimethyl disulphide, diethyl disulphide, methyl mercaptan, ethyl mercaptan, tert -butyl mercaptan, sec -butyl mercaptan, iso propyl mercaptan, n-propyl mercaptan cyclohexyl mercaptan, tetrahydrothiophene, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methylethylpyrazine, dimethyl selenide, and dimethyl diselenide.
  • the odorizing agents which can be used in the context of the present invention can be used pure, as a mixture of two or more of them in all proportions or alternatively diluted with other compounds compatible with the cryogenic fluid chosen from C 5 - C 6 (for example n-pentane, isopentane , cyclohexane, methylpentane, petroleum ether, as well as mixtures of two or more of them), sulfones, sulfoxides, and preferably chosen from alkanes.
  • C 5 - C 6 for example n-pentane, isopentane , cyclohexane, methylpentane, petroleum ether, as well as mixtures of two or more of them
  • sulfones for example n-pentane, isopentane , cyclohexane, methylpentane, petroleum ether, as well as mixtures of two or more of them
  • sulfones for example n-pent
  • odorizing agents in the context of the present invention alone or in mixtures of two or more of them in all proportions, optionally, but not preferably, diluted with one or more solvents as indicated above, in proportions of solvent(s) however not exceeding 20%, better still not exceeding 10% by weight of solvent relative to the total weight (odorizing agent(s)+solvent(s)).
  • the solvent is chosen from C 5 -C 6 alkanes whose physical properties allow easy handling, and typically those which are liquid at ambient temperature.
  • the solvent is iso -pentane which makes it possible in particular to lower the crystallization point of the odorizing composition and to approach the temperature of the cryogenic fluid, which is for example -162° C. for LNG ("Liquefied Natural Gas”), and therefore close to the melting temperature of isopentane (-160°C).
  • the odorizing agent that can be used in the context of the present invention can also comprise one or more additives chosen from heat stabilizers, dyes, antioxidants, such as for example those of the phenolic type, stable nitroxy radicals, for example of the tetramethylpiperidine oxide type (also known as TEMPO) and other derivatives, in particular described in “Synthetic Chemistry of Stable Nitroxides” by LB Volodarsky et al., CRC Press, (1993), ISBN: 0-8493-4590-1 .
  • additives chosen from heat stabilizers, dyes, antioxidants, such as for example those of the phenolic type, stable nitroxy radicals, for example of the tetramethylpiperidine oxide type (also known as TEMPO) and other derivatives, in particular described in “Synthetic Chemistry of Stable Nitroxides” by LB Volodarsky et al., CRC Press, (1993), ISBN: 0-8493-4590-1 .
  • the concentration of odorizing agent, when it is diluted in a solvent and/or when it is mixed with one or more additives can be comprised in large proportions, and generally between 0 1% and 100% by weight of odorizing agent relative to the total weight of the odorizing formulation.
  • the odorizing agent represents 100% of the odorizing formulation, i.e. the odorizing agent is used without solvent.
  • the odorizing agent will represent between 10 and 50% by weight of the odorizing formulation.
  • the odorizing agent is used in the absence of solvent and/or in the absence of any other additive, making it possible to minimize pollution of the cryogenic fluid.
  • the present invention consists of a process which continuously produces fine particles of a solid odorizing agent from said odorizing agent in liquid form, said fine particles of said solid odorizing agent then being continuously introduced into a cryogenic fluid in which they dissolve.
  • odorizing the cryogenic fluid it is preferred to carry out the process for odorizing the cryogenic fluid continuously, this embodiment being very particularly suitable for facilitating mixing and in particular ensuring the homogeneity of the odorized cryogenic fluid.
  • the odorization process according to the invention can also be carried out discontinuously, this embodiment typically being able to be carried out by introducing a charge of odorizing agent (optionally in the form of an odorizing formulation) into at least part of the cryogenic fluid to be odorized, for example in a stream of static cryogenic fluid, in a bypass or bypass, and the like, then dilution of this at least part of the odorized cryogenic fluid in said cryogenic fluid to be odorized.
  • the supply zone consists of any system allowing the odorant to be transferred from its storage to the buffer zone.
  • the supply zone is supplied, preferably continuously, with an odorizing agent which is in liquid or gaseous form, preferably in liquid form, said supply preferably being carried out at ambient temperature. Feeding the odorizing agent in the solid state is not preferred, for obvious reasons of handling and dosage, particularly when the odorization process according to the present invention is carried out in continuous mode.
  • the transfer of the odorizing agent into the supply zone can be carried out using a pump or any other pumping technology, or else by pressure difference between the storage and the buffer zone, or alternatively by pressure differential when injecting pre-loaded doses into intermediate storage. It is also possible to control the flow rate, for example using a flow meter, possibly combined with a control valve.
  • the odorizing agent can thus be supplied by any means known per se, for example by means of a pump or any other device making it possible to apply a pressure differential.
  • the supply pressure is between 0.1 MPa and 10 MPa, preferably between 0.1 MPa and 5 MPa.
  • the pressure values indicated above are values corresponding to absolute pressures.
  • the odorizing agent can be stored and used in a wide range of temperatures, for example being able to go from -100°C and +100°C, typically from -50°C to +60 °C.
  • the storage temperature is the temperature of the odorization site.
  • the storage pressure is most generally atmospheric pressure, the operating pressure possibly being different from the storage pressure in order to ensure the transport of the odorizing agent to the supply zone.
  • the supply of odorizing agent can be carried out by any device allowing the transfer of fluid (in the liquid or gaseous state), advantageously in a controlled manner, and preferably in a controlled and regulated manner.
  • the arrival in the buffer zone b) of the odorizing agent, typically when the latter is liquid, can be achieved by any means known per se, and for example by means of at least one or more elements chosen from cannula, nozzle , injector or any other means allowing the supply by drip or spray, and others, said aforementioned elements being able to be used alone or in combination of one or more of them.
  • This arrival in the buffer zone b) can also be carried out, typically when the odorizing agent is in gaseous form, by driving said odorizing agent (vapor pressure), possibly with a vector gas, as described for example in the international application WO1997019746 , or such as nitrogen, helium, argon, hydrogen, natural gas, methane, or any other light alkane, or even a part of the cryogenic fluid to be odorized, that -it having been previously vaporized, for example with a bypass system, as described for example in the patent US2058508 .
  • a vector gas as described for example in the international application WO1997019746 , or such as nitrogen, helium, argon, hydrogen, natural gas, methane, or any other light alkane, or even a part of the cryogenic fluid to be odorized, that -it having been previously vaporized, for example with a bypass system, as described for example in the patent US2058508 .
  • the odorizing agent can be thermostatically controlled in the supply zone a) and/or optionally upstream of said supply zone, in order to regulate/control the concentration of odorizing agent in the carrier gas .
  • the odorizing agent is injected in the form of a spray, said spray being able to be obtained by any technique known to those skilled in the art.
  • the supply zone is (are) equipped with means making it possible to maintain a temperature above the crystallization temperature of the odorizing agent, so that said odorizing agent is maintained in the fluid state (liquid or gaseous state), these means typically being one or more thermal insulation systems well known to those skilled in the art, and for example vacuum insulation, or circulation of a gas whose boiling point is less than or equal to the temperature of the cryogenic fluid.
  • thermal insulation systems well known to those skilled in the art, and for example vacuum insulation, or circulation of a gas whose boiling point is less than or equal to the temperature of the cryogenic fluid.
  • the thermal insulation can be achieved by heating the supply zone with a heat transfer fluid, possibly thermostatically controlled, by heating by means of a heating resistor, by induction, conduction, or the like.
  • the buffer zone b) makes it possible in particular to bring the odorizing agent, liquid or gaseous, to a temperature below 30° C. above the temperature of the cryogenic fluid.
  • This buffer zone has the effect of isolating the supply zone from the contact zone which is at the temperature of the cryogenic fluid.
  • the odorizing agent is, and remains, in a fluid state (liquid or gaseous) in the feed zone and is gradually brought to a temperature below 30°C above the temperature of the cryogenic fluid, or even at the temperature of the cryogenic fluid, on leaving the buffer zone b).
  • the temperature of the buffer zone is maintained, at least in part, at a temperature above the melting point of the odorizing agent, in order to avoid the cooling of said odorizing agent below its melting point. Crystallization, due to the proximity of the contact zone whose temperature, typically equal to that of the cryogenic fluid.
  • This temperature can be maintained by any means known to those skilled in the art, for example by means of a gas blanket in at least part of the supply zone and/or of the buffer zone, by preheating of the optionally formulated odorizing agent, heating of the supply zone and/or of the buffer zone, use of thermally insulating materials, and the like, or combination of two or more of the aforementioned techniques.
  • the gas sky is generally created by feeding a gas whose liquefaction point is less than or equal to the boiling temperature of the cryogenic fluid.
  • gases are nitrogen, argon, helium, hydrogen, methane, natural gas, and the like, and mixtures thereof.
  • This gas can be introduced into at least part of the supply zone and/or at least part of the buffer zone.
  • the rate of introduction of this gas is generally between 0.1 L.min -1 and 500 L.min -1 , preferably between 0.2 L.min -1 and 10 L.min -1 .
  • the gas flow can also make it possible to apply a pressure differential allowing a controlled and regulated supply of the odorizing agent in the supply zone.
  • the gas flow is slaved to a temperature measurement carried out within the supply zone.
  • the heating of the supply zone and/or the preheating of the odorizing agent makes it possible to maintain the temperature of the supply zone and/or at least part of the buffer zone at a temperature above the set point. fusion of the odorizing agent.
  • the buffer zone b) represents the space between the supply zone in which the odorizing agent is in liquid or vapor form, and the contact zone (or surface of the cryogenic fluid) in which the odorizing agent comes into contact with the cryogenic fluid.
  • This buffer zone has a temperature gradient between the temperature of the supply zone and the temperature of the contact zone.
  • the temperature gradient (typically cooling) is obtained by the cryogenic fluid considered.
  • the buffer zone b) can be equipped with mechanical assistance allowing improved transport of said odorizing agent to the cryogenic fluid, as described later in the description.
  • the introduction of the odorizing agent into the cryogenic fluid is carried out in the contact zone c).
  • Said contact zone c) is preferentially agitated in order to facilitate the dispersion of the odorizing agent to facilitate rapid dissolution in the medium.
  • This agitation can be generated by any means known to those skilled in the art, for example mechanical agitation, convection, circulation or recirculation by means of pumps or any other device allowing the generation of a flow at a greater or lesser rate.
  • the contact of the odorizing agent with the surface of the cryogenic fluid will be made in a flow of cryogenic fluid, thus making it possible to promote the dispersion of the odorizing agent, and this in a homogeneous manner, within the fluid. cryogenic which thus becomes an odorized cryogenic fluid.
  • the passage from the supply zone to the contact zone, through the buffer zone can be carried out by gravity and/or with mechanical assistance, making it possible to convey the odorizing agent, possibly in the form of odorizing formulation, towards the cryogenic fluid in order to ensure contact.
  • the method of the present invention thus has several advantages and more particularly that of not having to resort to the preparation of a pre-mixture containing the odorizing agent in a matrix as for example described in the patent application FR2201424 .
  • the method of the present invention is therefore easier to implement in that it does not require the use of additional solvent or else in small quantities, therefore no storage, and therefore little or no pollutant in the cryogenic fluid. odorized.
  • the addition of the odorizing agent in the cryogenic fluid is simplified, without the need for prior preparation of an odorizing concentrate, for example in a hydrocarbon such as propane, as described for example in FR2201424 .
  • the device for odorizing a cryogenic fluid described above can take various forms and aspects.
  • the figures 1 and 2 appended show two possible but non-limiting embodiments.
  • the Figure 1 represents an example of a device making it possible to implement the cryogenic fluid odorization method, according to the present invention.
  • This device comprises a supply zone (A), a buffer zone (B), and a contact zone (C).
  • the odorizing agent optionally in the form of an odorizing formulation, is introduced with a vector gas via the pipe (2) into the upper part of the endless screw (4) which is subjected to a rotational movement, via the motor (3 ), so that the odorizing agent (or the odorizing formulation) reaches, in the form of dispersed particles (5), the flow of cryogenic fluid (1) which flows in the direction indicated.
  • the Figure 2 represents another example of a device making it possible to implement the cryogenic fluid odorization method, according to the present invention, the device also comprising a supply zone (A), a buffer zone (B), and a contact zone (VS).
  • A supply zone
  • B buffer zone
  • VS contact zone
  • the odorizing agent (possibly in the form of an odorizing formulation) is introduced via line (2), with a vector gas via line (3), into the supply zone (A) comprising a heating resistor (4) intended to maintain a temperature above the solidification temperature of the odorizing agent (or of the odorizing formulation) which passes by gravity, via the buffer zone (B), into the contact zone (C) where it is dispersed ( e) (5) in the cryogenic fluid (1) flowing in the direction indicated.
  • a heating resistor (4) intended to maintain a temperature above the solidification temperature of the odorizing agent (or of the odorizing formulation) which passes by gravity, via the buffer zone (B), into the contact zone (C) where it is dispersed ( e) (5) in the cryogenic fluid (1) flowing in the direction indicated.
  • the odorizing device presented in this invention has many advantages, among which the great ease of use can be mentioned. Indeed, because of its small size and its easy installation, the device can be easily installed at the places where it is desired to practice the odorization of a cryogenic fluid. The method of the invention therefore finds a particularly advantageous application when it is implemented by means of the device according to the present invention.
  • cryogenic fluids can be implemented in many situations, such as, by way of non-limiting examples, when loading/filling tank trucks, tanks, boats, barges, gas cylinders, and others, from tanks, boats, barges or during the very process of liquefaction of the cryogenic fluid during transfer to/or within the storage, and others.
  • the odorization process according to the invention finds a very particularly advantageous application for the odorization of Liquefied Natural Gas (LNG), in particular when loading tank trucks or static or mobile storage from LNG carriers, by whether or not through one or more reservoirs.
  • LNG Liquefied Natural Gas
  • the odorizing agent belongs to the family of odorants conventionally used to odorize natural gas and is typically chosen from mercaptans and sulphides.
  • This embodiment is particularly suitable for the odorization of LNG, which then has a characteristic smell of gas, which allows the detection and identification of leaks during the transport, storage and use of said LNG, in order to warn of any danger linked to the accumulation of natural gas in the air.
  • the method of the present invention in particular when it is implemented for the odorization of LNG, it is now possible to dispense with gas odorization stations during the LNG regasification step. Indeed, the odorization process of the present invention can be carried out at a single centralized point.
  • This centralization thus makes it possible to limit the number of places involved in the storage and handling of odorizing agents and odorizing formulations and thus the risks of olfactory pollution, the costs associated with the maintenance of injection stations, and others.

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  • 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)
  • Cosmetics (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
  • Gas Separation By Absorption (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (11)

  1. Verfahren zur Odorierung eines Kryofluids im flüssigen Zustand, das zumindest die folgenden Schritte umfasst:
    a) kontinuierliches Einspeisen, bei einer Temperatur, die oberhalb der Temperatur des Kryofluids liegt und oberhalb der Kristallisationstemperatur des Odorierungsmittels liegt, eines Odorierungsmittels in flüssiger oder gasförmiger Form, vorzugsweise in flüssiger Form, in einen Einspeisebereich,
    b) Einspeisen des Odorierungsmittels in flüssiger oder gasförmiger Form aus dem Schritt a) in einen Pufferbereich, in welchem das Odorierungsmittel auf eine Temperatur gebracht wird, die um weniger als 30 °C über der Temperatur des Kryofluids liegt, und
    c) Einspeisen des Odorierungsmittel, welches im Schritt b) abgekühlt wurde, in den Kontaktbereich, in welchem das Odorierungsmittel in feststofflicher Form mit dem zu odorierenden Kryofluid in Kontakt kommt.
  2. Verfahren nach Anspruch 1, wobei die Flussrate des Odorierungsmittels im Kontaktbereich proportional zur Flussrate des Kryofluids ist, wobei die Flussrate des Odorierungsmittels im Kontaktbereich vorzugsweise von der Flussrate des Kryofluids abhängt.
  3. Verfahren nach Anspruch 1 oder Anspruch 2, wobei das Odorierungsmittel im Schritt b) auf eine Temperatur gebracht wird, die um weniger als 20 °C, mit noch größerem Vorzug weniger als 10 °C, über der Temperatur des zu odorierenden Kryofluids liegt.
  4. Verfahren nach einem beliebigen der vorhergehenden Ansprüche, wobei die Konzentration an Odorierungsmittel in dem Kryofluid im Bereich von 0,1 mg/m3 (n) bis 500 mg/m3 (n), vorzugsweise von 0,5 mg/m3 (n) bis 100 mg/m3 (n), mit noch größerem Vorzug von 0,5 mg/m3 (n) bis 50 mg/m3 (n) liegt.
  5. Verfahren nach einem beliebigen der vorhergehenden Ansprüche, wobei das Odorierungsmittel aus den Terpenen, den Alkoholen, den Phenolen, den Aldehyden, den Ethern, den Estern, den Fettsäuren, den Ketonen, den Lactonen, den Nitrilen, den pyrazinartigen Verbindungen, den Mercaptanen, den zyklischen Sulfiden, den Dialkylsulfiden, den Dialkyldisulfiden oder auch aus den Selenderivaten, allein oder in Mischungen von zweien oder mehreren, in beliebigen Anteilen, ausgewählt ist.
  6. Verfahren nach einem beliebigen der vorhergehenden Ansprüche, wobei das Odorierungsmittel aus Methyl- und Ethylsulfid, Dimethylsulfid, Diethylsulfid, Dimethyldisulfid, Diethyldisulfid, Methylmercaptan, Ethylmercaptan, tert.-Butylmercaptan, sec.-Butylmercaptan, Isopropylmercaptan, n-Propylmercaptan, Cyclohexylmercaptan, Tetrahydrothiophen, Methylacrylat, Ethylacrylat, Methylmethacrylat, Ethylmethacrylat, Methylethylpyrazin, Dimethylselenid und Dimethyldiselenid ausgewählt ist.
  7. Verfahren nach einem beliebigen der vorhergehenden Ansprüche, wobei das Odorierungsmittel in Reinform, in Mischung oder verdünnt mit anderen Lösungsmitteln verwendet wird, welche mit dem Kryofluid verträglich sind, wobei sie aus den C5-C6-Alkanen, den Sulfonen und den Sulfoxiden ausgewählt sind; in Lösungsmittelanteilen, die 20 % nicht überschreiten, nach Gewicht an Lösungsmittel unter Bezugnahme auf das Gesamtgewicht des/der Odorierungsmittel(s) und des/der Lösungsmittel(s).
  8. Verfahren nach einem beliebigen der vorhergehenden Ansprüche, wobei das Odorierungsmittel weiterhin einen oder mehrere Zusatzstoffe umfasst, die aus den Hitzestabilisatoren, den Farbstoffen, den Antioxidantien ausgewählt sind, um auf diese Weise eine odorierende Formulierung zu bilden.
  9. Verfahren nach einem beliebigen der vorhergehenden Ansprüche, wobei es sich bei dem Kryofluid um verflüssigtes Erdgas handelt.
  10. Vorrichtung zum Einleiten eines Odorierungsmittels in ein Kryofluid in flüssigem Zustand, wobei die Vorrichtung Folgendes umfasst:
    1) einen Einspeisebereich, in welchen Odorierungsmittel in flüssiger oder gasförmiger, vorzugsweise flüssiger, Form eingespeist wird,
    2) einen Pufferbereich, in welchem das flüssige oder gasförmige Odorierungsmittel auf eine Temperatur gebracht wird, die um weniger als 30 °C über der Temperatur des Kryofluids liegt, und
    3) einen Kontaktbereich, in welchem das Odorierungsmittel in flüssiger Form mit dem zu odorierenden Kryofluid in Kontakt kommt.
  11. Vorrichtung nach Anspruch 10, wobei der Pufferbereich b) mit einer mechanischen Hilfseinrichtung ausgestattet ist.
EP18722690.7A 2017-04-25 2018-04-18 Verfahren zur odorierung von kryogenen flüssigkeiten Active EP3615638B1 (de)

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HRP20221080TT HRP20221080T1 (hr) 2017-04-25 2018-04-18 Postupak kriogene odorizacije tekućina

Applications Claiming Priority (2)

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FR1753565A FR3065375B1 (fr) 2017-04-25 2017-04-25 Procede d'odorisation de fluide cryogenique
PCT/FR2018/050980 WO2018197783A1 (fr) 2017-04-25 2018-04-18 Procédé d'odorisation de fluide cryogénique

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EP3615638B1 true EP3615638B1 (de) 2022-07-27

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CA (1) CA3060506C (de)
DK (1) DK3615638T3 (de)
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FR (1) FR3065375B1 (de)
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CN117929677B (zh) * 2024-03-20 2024-06-14 普利莱（天津）燃气设备有限公司 一种多功能天然气加臭剂浓度分析仪和分析方法

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CA1006353A (en) * 1972-10-02 1977-03-08 David K. Mulliner Method and system for odorizing liquid natural gas with thiophene
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JPS5392802A (en) * 1977-01-25 1978-08-15 Bridgestone Liquefied Gas Co Addition of odorant to fuel gas
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US20010047621A1 (en) * 1999-06-29 2001-12-06 Joe Frank Arnold Injection system and method for odorizing natural gas
WO2002060411A2 (en) 2001-01-30 2002-08-08 Board Of Regents University Of Texas System Process for production of nanoparticles and microparticles by spray freezing into liquid
DE10240028A1 (de) * 2002-08-27 2004-03-11 Symrise Gmbh & Co. Kg Schwefelarme Odoriermittel für Flüssiggas
JP2004315566A (ja) * 2003-04-11 2004-11-11 Ishikawajima Harima Heavy Ind Co Ltd ガス付臭方法及び装置
FR2868790B1 (fr) 2004-04-08 2008-07-25 Arkema Sa Melange odorisant pour combustible gazeux inodore
DE102004050419A1 (de) 2004-10-15 2006-04-27 Linde Ag Odorierung von Wasserstoff on-board
JP5055883B2 (ja) * 2005-09-07 2012-10-24 トヨタ自動車株式会社 水素供給装置
FR2891841B1 (fr) 2005-10-11 2007-12-28 Arkema Sa Melange odorisant pour combustible gazeux inodore
FR2902798B1 (fr) 2006-06-26 2009-04-24 Arkema France Melange odorisant pour combustible gazeux inodore
CN202691601U (zh) * 2012-07-05 2013-01-23 北京普发兴业动力科技发展有限责任公司 高压压缩天然气管道的加臭装置
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KR20220017002A (ko) 2022-02-10
EP3615638A1 (de) 2020-03-04
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US11279895B2 (en) 2022-03-22
AU2018259133B2 (en) 2020-10-22
US20200157446A1 (en) 2020-05-21
US11814596B2 (en) 2023-11-14
FR3065375A1 (fr) 2018-10-26
SG11201909909YA (en) 2019-11-28
FR3065375B1 (fr) 2019-06-28
KR102519249B1 (ko) 2023-04-06
DK3615638T3 (da) 2022-09-05
WO2018197783A1 (fr) 2018-11-01
AU2018259133A1 (en) 2019-11-14
PL3615638T3 (pl) 2022-10-03
HRP20221080T1 (hr) 2022-12-23
CA3060506A1 (fr) 2018-11-01
CA3060506C (fr) 2023-09-26
PT3615638T (pt) 2022-09-08
KR20190126429A (ko) 2019-11-11
CN110520509B (zh) 2022-04-08
CN110520509A (zh) 2019-11-29

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