(19)
(11)EP 3 368 640 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
26.06.2019 Bulletin 2019/26

(21)Application number: 16785125.2

(22)Date of filing:  20.10.2016
(51)International Patent Classification (IPC): 
C10L 3/00(2006.01)
C10L 1/16(2006.01)
C10L 1/19(2006.01)
C10L 1/24(2006.01)
(86)International application number:
PCT/EP2016/075203
(87)International publication number:
WO 2017/072017 (04.05.2017 Gazette  2017/18)

(54)

FLUID COMPRISING METHANE AND A TRACER, AND PROCESSES FOR PRODUCING IT AND THE USE THEREOF

FLÜSSIGKEIT MIT METHAN UND TRACER UND VERFAHREN ZUR HERSTELLUNG DAVON UND VERWENDUNG DAVON

FLUIDE COMPRENANT DU MÉTHANE ET UN TRACEUR, ET SES PROCÉDÉS DE PRODUCTION ET SON UTILISATION


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 26.10.2015 EP 15191520

(43)Date of publication of application:
05.09.2018 Bulletin 2018/36

(73)Proprietor: Shell Internationale Research Maatschappij B.V.
2596 HR The Hague (NL)

(72)Inventors:
  • VAN DER VEER, Wouter Martinus
    2288 GK Rijswijk (NL)
  • MACDONALD, Stuart Meredith
    2596HR Den Haag (NL)

(74)Representative: Shell Legal Services IP 
PO Box 384
2501 CJ The Hague
2501 CJ The Hague (NL)


(56)References cited: : 
EP-A2- 0 203 661
US-A- 4 025 315
US-A1- 2004 072 051
US-A- 3 761 232
US-A1- 2003 051 394
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Field of the invention



    [0001] The invention relates to a fluid comprising methane and a tracer. This is also referred to as a labelled methane comprising fluid. The invention also relates to processes for producing labelled methane comprising fluids, and the use thereof. The invention especially relates to LNG comprising a tracer (labelled LNG), and processes for producing it, and the use of LNG comprising a tracer.

    Background to the invention



    [0002] Methane comprising fluids can be derived from a number of sources, such as natural gas or petroleum reservoirs, aerobic or anaerobic digestion of biological material, or from a synthetic source such as a Fischer-Tropsch process.

    [0003] Aerobic or anaerobic digestion of biological material can have many forms. It may, for example, concern aerobic or anaerobic digestion of dairy waste. Aerobic or anaerobic digestion of biological material results in a methane comprising fluid which may also be referred to as bio-methane, bio-gas or bio-fuel.

    [0004] The Fischer-Tropsch process can be used for the conversion of synthesis gas (from hydrocarbonaceous feed stocks) into liquid and/or solid hydrocarbons. Generally, the feed stock (e.g. natural gas, associated gas and/or coal-bed methane, heavy and/or residual oil fractions, coal, biomass) is converted in a first step into a mixture of hydrogen and carbon monoxide (this mixture is often referred to as synthesis gas or syngas).

    [0005] In this text the term natural gas is used to refer to methane comprising streams originating from any source.

    [0006] The term methane comprising fluid is used in this text to refer to fluids comprising at least 40 m/m% methane. The term in particular relates to natural gas fluids. Similarly, the terms methane comprising gas, methane comprising liquid, and methane comprising slush of liquid and solids, refer to gas, liquid, and slush of liquid and solids comprising at least 40 m/m% methane. A methane comprising fluid may comprise up to 100 m/m% methane, especially up to 99.9 m/m% methane, it may comprise up to 99 m/m% methane, it may comprise up to 90 m/m% methane. In the context of this invention a slush of liquid and solids is considered a fluid. The term methane comprising gas in particular relates to natural gas. The terms methane comprising liquid, and methane comprising slush of liquid and solids, in particular relate to LNG.

    [0007] Natural gas is a useful fuel source, as well as a source of various hydrocarbon compounds. It is often desirable to liquefy natural gas in a liquefied natural gas (LNG) plant at or near the source of a natural gas stream to enable compact storage of the natural gas and/or efficient transport of the natural gas over long distances. Natural gas can be more easily stored and transported in a liquid form than in a gaseous form because it occupies a smaller volume.

    [0008] Liquefied natural gas plants are well known in the field and comprise the following processing steps:
    • optionally treating the methane comprising stream by removing impurities in a treating stage, such as water, acid gases, mercury,
    • optionally removing natural gas liquids from the methane comprising stream in a NGL stage, such as ethane, propane, butane and heavier components,
    • cooling the methane comprising stream in one or more cooling stages, for instance a pre-cooling stage and a main cooling stage, and
    • optionally flashing the methane comprising stream in an end-flash stage and,
    • optionally, storing the liquefied natural gas in a storage tank.


    [0009] Methane comprising gas, such as natural gas is obtained from various sources. After liquefaction it is transported worldwide as LNG. LNG and regasified LNG are used for different purposes.

    [0010] Different countries and different purposes may have different requirements. This may relate to safety, proper use and/or tax regimes.

    [0011] There is a need for a possibility to trace methane comprising liquid and slush. There thus is a need for a method of labeling, or marking, methane comprising liquid and slush.

    Summary of the invention



    [0012] The present invention relates to a liquid comprising methane and a tracer. This can also be referred to as a traceable methane comprising fluid. This can also be referred to as a tagged, a marked, a fingerprinted or a labelled methane comprising fluid. The invention also relates to a slush of liquids and solids comprising methane and a tracer, i.e. a labelled methane comprising slush of liquids and solids. The invention especially relates to labelled LNG, whereby the LNG can be a liquid, or a slush of liquid and solids.

    [0013] A tracer compound may be used as a kind of fingerprint, or label. It may, for example, be used to indicate the source of the methane comprising fluid. Alternatively, it may be used to indicate the purpose of the methane comprising fluid, for example for domestic use or for industrial use. The presence of a tracer in a methane comprising fluid may be determined by means of any suitable commonly used gas detector. The tracer is methyl acetate.

    [0014] One tracer compound, or several kinds of tracer compounds, or one or more tracer compounds and one or more odorants can be used as a kind of fingerprint, or label.

    [0015] The present invention also relates to a process for preparing such a labelled liquid or slush by liquefying labelled methane comprising gas. The invention also relates to a process in which a tracer is added to a methane comprising liquid or slush.

    [0016] In more detail, the present invention relates to a labelled methane comprising fluid comprising:
    • a methane comprising fluid,
    • in the range of from 1 to 250 ppm, preferably 1 to 100 ppm, more preferably 1 to 50 ppm methyl acetate, calculated on the total mass of the labelled methane comprising fluid; whereby the labelled methane comprising fluid is a liquid, or a slush of liquid and solids, and
    whereby the labelled methane comprising fluid preferably is at a temperature in the range of from -62 °C to -185 °C, and at a pressure in the range of from 20 mbara to 120 bara, preferably 250 mbara to 76 bara.

    [0017] The present invention further relates to a process for preparing a labelled methane comprising fluid comprising in the range of from 1 to 250 ppm, preferably 1 to 100 ppm, more preferably 1 to 50 ppm methyl acetate, the process comprising the following step:
    1. a) adding methyl acetate to a methane comprising liquid, or a methane comprising slush of liquid and solids,
      whereby the liquid or slush comprising methane preferably is at a temperature in the range of from -62 °C to -185 °C, and at a pressure in the range of from 20 mbara to 120 bara, preferably 250 mbara to 76 bara.


    [0018] The present invention also relates to a process for preparing a labelled methane comprising fluid comprising in the range of from 1 to 250 ppm , preferably 1 to 100 ppm, more preferably 1 to 50 ppm methyl acetate, the process comprising the following steps:
    1. a) adding methyl acetate to a methane comprising gas, whereby the methane comprising gas preferably is at a temperature in the range of from -40 to +200 °C, more preferably -25 to +85 °C, and;
    2. b) liquefying the mixture obtained in step a) to a temperature in the range of from -62 °C to -185 °C and a pressure in the range of from 20 mbara to 120 bara, preferably 250 mbara to 76 bara.


    [0019] It was found that the present invention solves the need for a possibility to trace methane comprising liquid and slush.

    Detailed description of the invention



    [0020] The invention relates to a fluid comprising methane and a tracer. The invention also relates to processes for producing labelled methane comprising fluids, and the use thereof. The invention especially relates to LNG comprising a tracer (labelled LNG), and processes for producing it, and the use of LNG comprising a tracer. The tracer, and optionally an odorant, may, for example, be added at natural gas production facilities, at an LNG terminal, or at a retail station. The tracer, and optionally an odorant, may be added to a methane comprising fluid before or after liquefaction.

    Labelled methane comprising liquid or slush



    [0021] The present invention relates to a labelled methane comprising liquid, and to a labelled methane comprising slush of liquid and solids. The invention especially relates to labelled LNG, whereby the LNG can be a liquid, or a slush of liquid and solids.

    [0022] The present invention relates to a labelled methane comprising fluid comprising:
    • a methane comprising fluid,
    • in the range of from 1 to 250 ppm, preferably 1 to 100 ppm, more preferably 1 to 50 ppm methyl acetate, calculated on the total mass of the labelled methane comprising fluid. The labelled methane comprising fluid is a liquid, or a slush of liquid and solids. The labelled methane comprising fluid preferably is at a temperature in the range of from - 62 °C to -185 °C, and at a pressure in the range of from 20 mbara to 120 bara, preferably 250 mbara to 76 bara.


    [0023] When transporting, storing, or handling a methane comprising liquid or slush, normally boil off gas is created due to heat ingress. Thus, there is a need for an odorized methane comprising liquid or slush so that low concentrations of boil off gas in air can be easily detected by people.

    [0024] Odorants for a methane comprising liquid or slush, however, need to fulfill a number of requirements. The odorant needs to have a good solubility in a methane comprising liquid or slush at very low temperatures, even at temperatures around -162 °C, or even -185 °C. Furthermore, the odorant needs to remain in the methane comprising fluid when it transfers from the liquid phase to the gas phase. Additionally, the odorant needs to have a sufficiently low odor threshold value.

    [0025] In a preferred embodiment the labelled methane comprising fluid according to the invention additionally comprises an odorant. Highly suitable odorants are ethyl acrylate, ethyl mercaptan, and a mixture thereof.

    [0026] Preferably the labelled methane comprising fluid additionally comprises:
    • in the range of from 1 to 100 ppm of an odorant,
    • in the range of from 0.1 to 10 m/m% of a carrier, calculated on the total mass of the labelled methane comprising fluid. The carrier is propane, n-butane, iso-butane, or a mixture of two or more thereof. The odorant is ethyl acrylate, ethyl mercaptan, or a mixture thereof.


    [0027] Odorant and carrier preferably are used in a ratio of from 1:20 to 1:50000, more preferably 1:100 to 1:5000, even more preferably 1:650 to 1:1500.

    [0028] Preferably the labelled methane comprising fluid comprises 2 to 10 ppm odorant, and preferably 0.2 to 1 m/m% carrier, calculated on the total mass of the labelled methane comprising fluid.

    [0029] Preferably the labelled methane comprising fluid comprises 4 to 6 ppm odorant, and preferably 0.4 to 0.6 m/m% carrier, calculated on the total mass of the labelled methane comprising fluid.

    [0030] Preferably the carrier is iso-butane.

    [0031] Preferably the odorant is ethyl acrylate or a mixture of ethyl acrylate and ethyl mercaptan.

    Process in which a tracer is added to liquid or slush



    [0032] The present invention also relates to a process in which a tracer is added to a methane comprising liquid or slush. Preferably a labelled methane comprising liquid or slush according to the invention is obtained. All embodiments of the labelled methane comprising liquid or slush as described above can be obtained with this process.

    [0033] The invention relates to a process for preparing a labelled methane comprising fluid comprising in the range of from 1 to 250 ppm, preferably 1 to 100 ppm, more preferably 1 to 50 ppm methyl acetate, the process comprising the following step:
    1. a) adding methyl acetate to a methane comprising liquid, or
      a methane comprising slush of liquid and solids,
      whereby the liquid or slush comprising methane preferably is at a temperature in the range of from -62 °C to -185 °C, and at a pressure in the range of from 20 mbara to 120 bara, preferably 250 mbara to 76 bara.


    [0034] Preferably methyl acetate, an odorant and a carrier for the odorant are added to a methane comprising liquid or slush. Preferably the process comprises the following step:
    1. a) adding methyl acetate, and in the range of from 1 to 100 ppm of an odorant, and in the range of from 0.1 to 10 m/m% of a carrier to a methane comprising liquid, or a methane comprising slush of liquid and solids,
      whereby the odorant and carrier are added separately and/or mixed, and
      whereby the methyl acetate is added separately and/or mixed with odorant and/or carrier, and
      whereby the carrier is propane, n-butane, iso-butane, or a mixture of two or more thereof, and
      whereby the odorant is ethyl acrylate, ethyl mercaptan, or a mixture thereof.


    [0035] Odorant and carrier preferably are used in a ratio of from 1:20 to 1:50000, more preferably 1:100 to 1:5000, even more preferably 1:650 to 1:1500.

    [0036] Preferably the obtained labelled methane comprising fluid comprises 2 to 10 ppm odorant, and preferably 0.2 to 1 m/m% carrier, calculated on the total mass of the labelled methane comprising fluid.

    [0037] Preferably the obtained labelled methane comprising fluid comprises 4 to 6 ppm odorant, and preferably 0.4 to 0.6 m/m% carrier, calculated on the total mass of the labelled methane comprising fluid.

    [0038] Preferably the carrier is iso-butane.

    [0039] Preferably the odorant is ethyl acrylate or a mixture of ethyl acrylate and ethyl mercaptan.

    [0040] Preferably step a) of the process is performed by:

    a1) adding odorant to carrier and

    a2) adding at least a part of the mixture obtained in step a1) to a methane comprising liquid, or a methane comprising slush of liquid and solids, and
    adding methyl acetate separately and/or mixed with odorant and carrier.



    [0041] Preferably a stream comprising a tracer and/or an odorant is added to a gas stream, a liquid stream, or a stream of a slush of liquid and solids, using a flow controller, e.g. a control valve, or an injection pump, e.g. a fixed volume injection pump, and a PLC (programmable logic controller).

    Process in which a tracer is added to gas, followed by liquefaction



    [0042] The present invention also relates to a process for preparing a labelled liquid or slush by liquefying a methane comprising gas which comprises a tracer. Preferably a labelled methane comprising liquid or slush according to the invention is obtained. All embodiments of the labelled methane comprising liquid or slush as described above can be obtained with this process.

    [0043] The invention relates to a process for preparing a labelled methane comprising fluid comprising in the range of from 1 to 250 ppm , preferably 1 to 100 ppm, more preferably 1 to 50 ppm methyl acetate, the process comprising the following steps:
    1. a) adding methyl acetate to a methane comprising gas, whereby the methane comprising gas preferably is at a temperature in the range of from -40 to +200 °C, more preferably -25 to +85 °C, and;
    2. b) liquefying the mixture obtained in step a) to a temperature in the range of from -62 °C to -185 °C and a pressure in the range of from 20 mbara to 120 bara, preferably 250 mbara to 76 bara.


    [0044] Preferably step a) is performed as follows:
    1. a) adding methyl acetate, and in the range of from 1 to 100 ppm of an odorant, and in the range of from 0.1 to 10 m/m% of a carrier to a methane comprising gas,
      whereby the odorant and carrier are added separately and/or mixed, and
      whereby the methyl acetate is added separately and/or mixed with odorant and/or carrier, and
      whereby the carrier is propane, n-butane, iso-butane, or a mixture of two or more thereof, and
      whereby the odorant is ethyl acrylate, ethyl mercaptan, or a mixture thereof.


    [0045] Odorant and carrier preferably are used in a ratio of from 1:20 to 1:50000, more preferably 1:100 to 1:5000, even more preferably 1:650 to 1:1500.

    [0046] Preferably the obtained labelled methane comprising fluid comprises 2 to 10 ppm odorant, and preferably 0.2 to 1 m/m% carrier, calculated on the total mass of the labelled methane comprising fluid.

    [0047] Preferably the obtained labelled methane comprising fluid comprises 4 to 6 ppm odorant, and preferably 0.4 to 0.6 m/m% carrier, calculated on the total mass of the labelled methane comprising fluid.

    [0048] Preferably the carrier is iso-butane.

    [0049] Preferably the odorant is ethyl acrylate or a mixture of ethyl acrylate and ethyl mercaptan.

    [0050] Preferably steps a) and b) of the process are performed by:

    a1) adding odorant to carrier, and

    a2) adding at least a part of the mixture obtained in step a1) to a methane comprising gas,
    whereby the methane comprising gas preferably is at a temperature in the range of from -40 to +200 °C, more preferably -25 to +85 °C, and
    adding the methyl acetate separately and/or mixed with odorant and carrier, and

    b) liquefying the mixture obtained in step a2) to a temperature in the range of from -62 °C to -185 °C and a pressure in the range of from 20 mbara to 120 bara, preferably 250 mbara to 76 bara.



    [0051] Preferably a stream comprising a tracer and/or an odorant is added to a gas stream, a liquid stream, or a stream of a slush of liquid and solids, using a flow controller, e.g. a control valve, or an injection pump, e.g. a fixed volume injection pump, and a PLC (programmable logic controller).

    Use



    [0052] The invention further relates to the use of a labelled methane comprising fluid according to the invention, or prepared in a process according to the invention, as fuel in automotive industry, marine industry, or for power generation.

    Examples



    [0053] Labelled LNG samples were prepared according to the invention. Additional samples were prepared by using different odorants. A tracer or an odor was added to natural gas, followed by liquefaction in a cryostat. The labelled or odorized natural gas was analyzed before and after liquefaction.

    [0054] The results are summarized in the following tables.
    Sample preparation:
    SampleOdorantConcentration added to natural gas [ppm]Concentration in liquid phase after liquefaction [ppb]
    A Ethyl acrylate 5 550 ± 12 % RSD
    B Ethyl acrylate 5 5000 ± 2.6% RSD
    C Methyl acrylate 5 350 ± 8% RSD
    D Methyl acetate 5 4000 ± 20% RSD
    E t-butyl mercaptan 1 1000 ± 20% RSD
    F t-butyl mercaptan 5 2063 ± 20% RSD
    G diethyl sulphide 5 4550 ± 4% RSD
    H ethyl mercaptan 1 969 ± 3.8% RSD
    I ethyl mercaptan 5 4803 ± 4.6% RSD
    J dimethyl ether 5000 500000 ± 17% RSD


    [0055] From the sample preparation follows that methyl acetate dissolves well at low temperatures. It also follows that some odorants do not dissolve well at very low temperatures. They crystallize out.

    [0056] Measurements were performed on the labelled or odorized natural gas before liquefaction. In other words, measurements were performed on labelled or odorized NG. The measurements were performed using a gas detector and by smelling.
    Measurements on labelled or odorized natural gas using a gas cylinder:
    SampleAmount of odorant (using gas detector) [ppm]Odor at 20% LEL
    A 5 ± 0.3 % RSD Yes
    B 5 ± 0.1 % RSD Yes
    C 5 ± 0.2 % RSD No
    D 5 ± 0.3 % RSD No
    E 1 ± 0.8 % RSD Yes
    F 5 ± 0.3 % RSD Yes
    G 5 ± 0.1 % RSD Insufficient data
    H 1 ± 0.7 % RSD Yes
    I 5 ± 0.3 % RSD Yes
    J 4947 ± 0.1 % RSD No
    "20% LEL" stands for 20% of lower explosion limit.
    "Odor at 20% LEL" stands for whether or not odor could be smelled at 20% LEL.
    "RSD" stands for relative standard deviation.


    [0057] Measurements were performed on the labelled or odorized natural gas which was liquefied in the cryostat. In other words, measurements were performed on labelled or odorized LNG. The measurements were performed using a gas detector and by smelling.

    [0058] In the headspace of the cryostat none of the odorants was detected by either gas detection or smelling.
    Measurements on labelled or odorized LNG in cryostat:
    SampleTemperature of liquid [K]Pressure [PSI]Odor at 20% LEL
    A 114 18 Yes
    B 124 35 Yes
    C 114 18 Yes
    D 114 18 No
    E 114 18 Yes
    F 114 18 Yes
    G 114 18 Insufficient data
    H 114 18 Yes
    I 114 18 Yes
    J 114 18 No
    Measurements on boil off gas of the odorized LNG:
    SampleBoil off gas (using gas detector) [ppb]Odor at 20% LEL
    A 0 Insufficient data
    B   Yes
    C   No
    D 100 ± 8 RSD No
    E   No
    F   No
    G   No
    H   Insufficient data
    I   Yes
    J   No


    [0059] From the above data follows that methyl acetate is suitable to be used as tracer. From the above data is clear that ethyl acrylate and ethyl mercaptan are suitable to be used as odorant for LNG.


    Claims

    1. A labelled methane comprising fluid comprising:

    - a methane comprising fluid,

    - in the range of from 1 to 250 ppm, preferably 1 to 100 ppm, more preferably 1 to 50 ppm methyl acetate, calculated on the total mass of the labelled methane comprising fluid;
    whereby the labelled methane comprising fluid is a liquid,
    or a slush of liquid and solids, and
    whereby the labelled methane comprising fluid preferably is at a temperature in the range of from -62 °C to -185 °C,
    and at a pressure in the range of from 20 mbara to 120 bara, preferably 250 mbara to 76 bara.


     
    2. A labelled methane comprising fluid according to claim 1, whereby the labelled methane comprising fluid additionally comprises:

    - in the range of from 1 to 100 ppm of an odorant,

    - in the range of from 0.1 to 10 m/m% of a carrier, calculated on the total mass of the labelled methane comprising fluid;
    whereby the carrier is propane, n-butane, iso-butane, or a mixture of two or more thereof, and
    whereby the odorant is ethyl acrylate, ethyl mercaptan, or
    a mixture thereof.


     
    3. A labelled methane comprising fluid according to claim 2, whereby the labelled methane comprising fluid comprises 2 to 10 ppm odorant, and preferably 0.2 to 1 m/m% carrier, calculated on the total mass of the labelled methane comprising fluid.
     
    4. A labelled methane comprising fluid according to claim 2 or 3, whereby the labelled methane comprising fluid comprises 4 to 6 ppm odorant, and preferably 0.4 to 0.6 m/m% carrier, calculated on the total mass of the labelled methane comprising fluid.
     
    5. A labelled methane comprising fluid according to any one of claims 2 to 4, whereby the carrier is iso-butane.
     
    6. A labelled methane comprising fluid according to any one of claims 2 to 5, whereby the odorant is ethyl acrylate or a mixture of ethyl acrylate and ethyl mercaptan.
     
    7. A process for preparing a labelled methane comprising fluid comprising in the range of from 1 to 250 ppm, preferably 1 to 100 ppm, more preferably 1 to 50 ppm methyl acetate, the process comprising the following step:

    a) adding methyl acetate to a methane comprising liquid, or
    a methane comprising slush of liquid and solids,
    whereby the liquid or slush comprising methane preferably is at a temperature in the range of from -62 °C to -185 °C, and at a pressure in the range of from 20 mbara to 120 bara, preferably 250 mbara to 76 bara.


     
    8. A process according to claim 7, comprising the following step:

    a) adding methyl acetate, and in the range of from 1 to 100 ppm of an odorant, and in the range of from 0.1 to 10 m/m% of a carrier to a methane comprising liquid, or a methane comprising slush of liquid and solids,
    whereby the odorant and carrier are added separately and/or mixed, and
    whereby the methyl acetate is added separately and/or mixed with odorant and/or carrier, and
    whereby the carrier is propane, n-butane, iso-butane, or a mixture of two or more thereof, and
    whereby the odorant is ethyl acrylate, ethyl mercaptan, or a mixture thereof.


     
    9. A process according to claim 8, comprising the following steps:

    a1) adding odorant to carrier and

    a2) adding at least a part of the mixture obtained in step a1) to a methane comprising liquid, or a methane comprising slush of liquid and solids, and
    adding methyl acetate separately and/or mixed with odorant and carrier.


     
    10. A process for preparing a labelled methane comprising fluid comprising in the range of from 1 to 250 ppm , preferably 1 to 100 ppm, more preferably 1 to 50 ppm methyl acetate, the process comprising the following steps:

    a) adding methyl acetate to a methane comprising gas, whereby the methane comprising gas preferably is at a temperature in the range of from -40 to +200 °C, more preferably -25 to +85 °C, and;

    b) liquefying the mixture obtained in step a) to a temperature in the range of from -62 °C to -185 °C and a pressure in the range of from 20 mbara to 120 bara, preferably 250 mbara to 76 bara.


     
    11. A process according to claim 10, comprising the following steps:

    a) adding methyl acetate, and in the range of from 1 to 100 ppm of an odorant, and in the range of from 0.1 to 10 m/m% of a carrier to a methane comprising gas,
    whereby the odorant and carrier are added separately and/or mixed, and
    whereby the methyl acetate is added separately and/or mixed with odorant and/or carrier, and
    whereby the carrier is propane, n-butane, iso-butane, or a mixture of two or more thereof, and
    whereby the odorant is ethyl acrylate, ethyl mercaptan, or a mixture thereof.


     
    12. A process according to claim 11, comprising the following steps:

    a1) adding odorant to carrier, and

    a2) adding at least a part of the mixture obtained in step a1) to a methane comprising gas,
    whereby the methane comprising gas preferably is at a temperature in the range of from -40 to +200 °C, more preferably -25 to +85 °C, and
    adding the methyl acetate separately and/or mixed with odorant and carrier, and

    b) liquefying the mixture obtained in step a2) to a temperature in the range of from -62 °C to -185 °C and a pressure in the range of from 20 mbara to 120 bara, preferably 250 mbara to 76 bara.


     
    13. A process according to any one of claims 7 to 12, wherein a stream comprising a tracer and/or an odorant is added to a gas stream, a liquid stream, or a stream of a slush of liquid and solids, using a flow controller or an injection pump and a PLC (programmable logic controller).
     
    14. Use of a labelled methane comprising fluid according to any one of claims 1 to 6, or an odorized methane comprising fluid prepared according to any one of claims 7 to 13, as fuel in automotive industry, marine industry, or for power generation.
     


    Ansprüche

    1. Markiertes Methan, das Fluid umfasst, umfassend:

    - ein Methan, das Fluid umfasst,

    - im Bereich von 1 bis 250 ppm, vorzugsweise von 1 bis 100 ppm, bevorzugter von 1 bis 50 ppm Methylacetat, berechnet auf die Gesamtmasse des markierten Methans, das Fluid umfasst;
    wobei das markierte Methan, das Fluid umfasst, eine Flüssigkeit oder ein Schlamm von Flüssigkeit und Feststoffen ist, und
    wobei das markierte Methan, das Fluid umfasst, vorzugsweise bei einer Temperatur im Bereich von -62 °C bis -185 °C, und bei einem Druck im Bereich von 20 mbara bis 120 bara, vorzugsweise von 250 mbara bis 76 bara liegt.


     
    2. Markiertes Methan, umfassend Fluid nach Anspruch 1, wobei das markierte Methan, das Fluid umfasst, zusätzlich Folgendes umfasst:

    - im Bereich von 1 bis 100 ppm ein Odormittel,

    - im Bereich von 0,1 bis 10 m/m% einen Träger, berechnet auf die Gesamtmasse des markierten Methans, das Fluid umfasst;
    wobei der Träger Propan, n-Butan, Iso-Butan oder eine Mischung aus zwei oder mehr davon ist; und
    und wobei das Odormittel Ethylacrylat, Ethylmercaptan oder eine Mischung davon ist.


     
    3. Markiertes Methan, umfassend Fluid nach Anspruch 2, wobei das markierte Methan, das Fluid umfasst, Folgendes umfasst: von 2 bis 10 ppm Odormittel und vorzugsweise von 0,2 bis 1 Gew.-% eines Trägers, berechnet auf die Gesamtmasse des markierten Methans, das Fluid umfasst.
     
    4. Markiertes Methan, das Fluid umfasst, nach Anspruch 2 oder 3, wobei das markierte Methan, das Fluid umfasst, Folgendes umfasst: von 4 bis 6 ppm Odormittel und vorzugsweise von 0,4 bis 0,6 Gew.-% eines Trägers, berechnet auf die Gesamtmasse des markierten Methans, das Fluid umfasst.
     
    5. Markiertes Methan, das Fluid umfasst, nach einem der Ansprüche 2 bis 4, wobei der Träger Isobutan ist.
     
    6. Markiertes Methan, das Fluid umfasst, nach einem der Ansprüche 2 bis 5, wobei das Odormittel Ethylacrylat oder eine Mischung aus Ethylacrylat und Ethylmercaptan ist.
     
    7. Verfahren zum Herstellen eines markierten Methans, das Fluid umfasst, das im Bereich von 1 bis 250 ppm, vorzugsweise von 1 bis 100 ppm, bevorzugter von 1 bis 50 ppm Methylacetat umfasst, wobei das Verfahren den folgenden Schritt umfasst:

    a) Hinzufügen von Methylacetat zu einem Methan, das Flüssigkeit umfasst, oder zu einem Methan, das Schlamm von Flüssigkeit und Feststoffen umfasst,
    wobei die Flüssigkeit oder der Schlamm, die Methan umfassen, vorzugsweise bei einer Temperatur im Bereich von -62 °C bis -185 °C und bei einem Druck im Bereich von 20 mbara bis 120 bara, vorzugsweise von 250 mbara bis 76 bara liegen.


     
    8. Verfahren nach Anspruch 7, umfassend den folgenden Schritt:

    a) Hinzufügen von Methylacetat und im Bereich von 1 bis 100 ppm eines Odormittels und im Bereich von 0,1 bis 10 Gew.-% eines Trägers zu einem Methan, das Flüssigkeit umfasst, oder einem Methan, das Schlamm von Flüssigkeit und Feststoffen umfasst,
    wobei das Odormittel und der Träger getrennt und/oder gemischt zugegeben werden, und
    wobei das Methylacetat getrennt und/oder mit Odormittel und/oder Träger gemischt wird, und
    wobei der Träger Propan, n-Butan, Iso-Butan oder eine Mischung aus zwei oder mehr davon ist; und
    und wobei das Odormittel Ethylacrylat, Ethylmercaptan oder eine Mischung davon ist.


     
    9. Verfahren nach Anspruch 8, umfassend die folgenden Schritte:

    a1) Hinzufügen von Odormittel zum Träger und

    a2) Hinzufügen mindestens eines Teils der in Schritt a1) erhaltenen Mischung zu einer Methan umfassenden Flüssigkeit oder einem Methan, das Schlamm von Flüssigkeit und Feststoffen umfasst, und
    Hinzufügen von Methylacetat getrennt und/oder gemischt mit Odormittel und Träger.


     
    10. Verfahren zum Herstellen eines markierten Methans, das Fluid umfasst, das im Bereich von 1 bis 250 ppm, vorzugsweise von 1 bis 100 ppm, bevorzugter von 1 bis 50 ppm Methylacetat umfasst, wobei das Verfahren die folgenden Schritte umfasst:

    a) Hinzufügen von Methylacetat zu einem Methan, das Gas umfasst,
    wobei das Gas enthaltende Methan vorzugsweise bei einer Temperatur im Bereich von -40 bis +200 °C, bevorzugter von -25 bis +85 °C liegt, und;

    b) Verflüssigen der in Schritt a) erhaltenen Mischung auf eine Temperatur im Bereich von -62 °C bis -185 °C und einen Druck im Bereich von 20 mbara bis 120 bara, vorzugsweise von 250 mbara bis 76 bara.


     
    11. Verfahren nach Anspruch 10, umfassend die folgenden Schritte:

    a) Hinzufügen von Methylacetat und im Bereich von 1 bis 100 ppm eines Odormittels und im Bereich von 0,1 bis 10 Gew.-% eines Trägers zu einem Methan, das Gas umfasst,
    wobei das Odormittel und der Träger getrennt und/oder gemischt zugegeben werden, und
    wobei das Methylacetat getrennt und/oder mit Odormittel und/oder Träger gemischt wird, und
    wobei der Träger Propan, n-Butan, Iso-Butan oder eine Mischung aus zwei oder mehr davon ist; und
    und wobei das Odormittel Ethylacrylat, Ethylmercaptan oder eine Mischung davon ist.


     
    12. Verfahren nach Anspruch 11, umfassend die folgenden Schritte:

    a1) Hinzufügen von Odormittel zum Träger, und

    a2) Hinzufügen mindestens eines Teils der in Schritt a1) erhaltenen Mischung zu einem Methan, das Gas umfasst,
    wobei das Methan, das Gas umfasst, vorzugsweise bei einer Temperatur im Bereich von -40 bis +200 °C,
    bevorzugter von -25 bis +85 °C liegt, und
    Hinzufügen des Methylacetats getrennt und/oder gemischt mit Odormittel und Träger, und

    b) Verflüssigen der in Schritt a2) erhaltenen Mischung auf eine Temperatur im Bereich von -62 °C bis -185 °C und einen Druck im Bereich von 20 mbara bis 120 bara, vorzugsweise von 250 mbara bis 76 bara.


     
    13. Verfahren nach einem der Ansprüche 7 bis 12, wobei ein Strom, der einen Tracer und/oder ein Duftstoff umfasst, unter Verwendung einer Durchflusssteuerung oder einer Einspritzpumpe und einer SPS (speicherprogrammierbare Steuerung) zu einem Gasstrom, einem Flüssigkeitsstrom oder einem Strom eines Schlamms aus Flüssigkeit und Feststoffen hinzugefügt wird.
     
    14. Verwenden eines markierten Methans, das ein Fluid nach einem der Ansprüche 1 bis 6 umfasst, oder eines odorierten Methans, das ein Fluid umfasst, das nach einem der Ansprüche 7 bis 13 hergestellt wurde, als Kraftstoff in der Automobilindustrie, Schiffbauindustrie oder zur Energieerzeugung.
     


    Revendications

    1. Fluide marqué contenant du méthane, comprenant :

    - un fluide contenant du méthane,

    - une proportion de 1 à 250 ppm, de préférence de 1 à 100 ppm, plus préférablement de 1 à 50 ppm d'acétate de méthyle, calculée sur la base de la masse totale du fluide marqué contenant du méthane ;
    le fluide marqué contenant du méthane étant un liquide ou une boue de liquide et de solides, et
    le fluide marqué contenant du méthane étant de préférence à une température comprise entre -62 et - 185 °C et à une pression comprise entre 20 mbara et 120 bara, de préférence entre 250 mbara et 76 bara.


     
    2. Fluide marqué contenant du méthane selon la revendication 1, dans lequel le fluide marqué comprenant du méthane comprend en outre :

    - une proportion de 1 à 100 ppm d'une substance odorante,

    - une proportion de 0,1 à 10 m/m% d'un support,
    calculée sur la masse totale du fluide marqué contenant du méthane ;
    le support étant du propane, du n-butane, de l'isobutane ou un mélange d'au moins deux de ceux-ci, et
    la substance odorante étant l'acrylate d'éthyle, l'éthylmercaptan ou un mélange de ceux-ci.


     
    3. Fluide marqué contenant du méthane selon la revendication 2, dans lequel le fluide marqué contenant du méthane comprend 2 à 10 ppm de substance odorante et de préférence 0,2 à 1 m/m% de support, calculé sur la base de la masse totale du fluide marqué contenant du méthane.
     
    4. Fluide marqué contenant du méthane selon la revendication 2 ou 3, dans lequel le fluide marqué contenant du méthane comprend 4 à 6 ppm de substance odorante et de préférence 0,4 à 0,6 m/m% de support, calculé sur la base de la masse totale du fluide marqué contenant du méthane.
     
    5. Fluide marqué contenant du méthane selon l'une quelconque des revendications 2 à 4, dans lequel le support est l'isobutane.
     
    6. Fluide marqué contenant du méthane selon l'une quelconque des revendications 2 à 5, dans lequel la substance odorante est l'acrylate d'éthyle ou un mélange d'acrylate d'éthyle et d'éthylmercaptan.
     
    7. Procédé de préparation d'un fluide marqué contenant du méthane, comprenant une proportion de 1 à 250 ppm, de préférence de 1 à 100 ppm, plus préférablement de 1 à 50 ppm d'acétate de méthyle, le procédé comprenant l'étape suivante :

    a) ajout de l'acétate de méthyle à un liquide contenant du méthane ou à une boue de liquide et de solides contenant du méthane,
    le liquide ou la boue contenant du méthane étant de préférence à une température comprise entre -62 et - 185 °C et à une pression comprise entre 20 mbara et 120 bara, de préférence entre 250 mbara et 76 bara.


     
    8. Procédé selon la revendication 7, comprenant l'étape suivante :

    a) ajout de l'acétate de méthyle, dans une proportion de 1 à 100 ppm d'une substance odorante, et dans une proportion de 0,1 à 10 m/m% d'un support, à un liquide contenant du méthane ou à une boue de liquide ou de solides contenant du méthane,
    la substance odorante et le support étant ajoutés séparément et/ou mélangés, et
    l'acétate de méthyle étant ajouté séparément et/ou mélangé avec une substance odorante et/ou un support, et le support étant du propane, du n-butane, de l'isobutane ou un mélange d'au moins deux de ceux-ci, et
    la substance odorante étant l'acrylate d'éthyle, l'éthylmercaptan ou un mélange de ceux-ci.


     
    9. Procédé selon la revendication 8, comprenant les étapes suivantes :

    a1) ajout de substance odorante au support,

    a2) ajout d'au moins une partie du mélange obtenu à l'étape a1) à un liquide contenant du méthane ou à une boue de liquide ou de solides contenant du méthane, et ajout de l'acétate de méthyle séparément et/ou en mélange avec une substance odorante et un support.


     
    10. Procédé de préparation d'un fluide marqué contenant du méthane, comprenant une proportion de 1 à 250 ppm, de préférence de 1 à 100 ppm, plus préférablement de 1 à 50 ppm d'acétate de méthyle, le procédé comprenant les étapes suivantes :

    a) ajout de l'acétate de méthyle à un gaz contenant du méthane,
    le gaz contenant du méthane étant de préférence à une température comprise entre -40 et +200 °C, plus préférablement entre -25 et +85 °C, et

    b) liquéfaction du mélange obtenu à l'étape a) à une température comprise entre -62 et -185 °C et à une pression comprise entre 20 mbara et 120 bara, de préférence entre 250 mbara et 76 bara.


     
    11. Procédé selon la revendication 10, comprenant les étapes suivantes :

    a) ajout de l'acétate de méthyle, dans une proportion de 1 à 100 ppm d'une substance odorante, et dans une proportion de 0,1 à 10 m/m% d'un support, à un gaz contenant du méthane,
    la substance odorante et le support étant ajoutés séparément et/ou mélangés, et
    l'acétate de méthyle étant ajouté séparément et/ou mélangé avec une substance odorante et/ou un support, et le support étant du propane, du n-butane, de l'isobutane ou un mélange d'au moins deux de ceux-ci, et
    la substance odorante étant l'acrylate d'éthyle, l'éthylmercaptan ou un mélange de ceux-ci.


     
    12. Procédé selon la revendication 11, comprenant les étapes suivantes :

    a1) ajout de substance odorante au support,

    a2) ajout d'au moins une partie du mélange obtenu à l'étape a1) à un gaz contenant du méthane,
    le gaz contenant du méthane étant de préférence à une température comprise entre -40 et +200 °C, plus préférablement entre -25 et +85 °C, et
    ajout de l'acétate de méthyle séparément et/ou en mélange avec une substance odorante et un support, et

    b) liquéfaction du mélange obtenu à l'étape a2) à une température comprise entre -62 et -185 °C et à une pression comprise entre 20 mbara et 120 bara, de préférence entre 250 mbara et 76 bara.


     
    13. Procédé selon l'une quelconque des revendications 7 à 12, dans lequel un flux comprenant un traceur et/ou une substance odorante est ajouté à un flux gazeux, un flux liquide, ou à un flux d'une boue de liquide et de solides, en utilisant un régulateur de flux ou une pompe d'injection et un automate programmable.
     
    14. Utilisation d'un fluide marqué contenant du méthane selon l'une quelconque des revendications 1 à 6, ou d'un fluide odorisé contenant du méthane, préparé selon l'une quelconque des revendications 7 à 13, comme carburant dans l'industrie automobile, dans la marine ou pour la production d'énergie.