Fluid comprising methane and a tracer, and processes for producing it and the use thereof

Abstract

A labelled methane, such as LNG, has methane and a tracer, in the form of a slush of liquids and solids. The invention especially relates to LNG having a tracer. The labelled methane may comprise, in addition to the tracer, an odorant, and a carrier for the odorant. The odorant is ethyl acetate and/or ethyl mercaptan. The carrier for the odorant is propane, n-butane, iso-butane, or a mixture of two or more thereof. A process for preparing the liquid or slush involves liquefying a gas comprising methane and tracer.

Claims

1. A labelled methane comprising fluid comprising: a methane comprising fluid, methyl acetate, in a range of from 1 to 250 ppm, calculated on the total mass of the labelled methane comprising fluid; an odorant in a range of from 1 to 100 ppm, and a carrier in a range of from 0.1 to 10 m/m %, calculated on the total mass of the labelled methane comprising fluid; wherein the carrier is propane, n-butane, iso-butane, or a mixture of two or more thereof, and wherein the odorant is ethyl acrylate, ethyl mercaptan, or a mixture thereof, wherein the labelled methane comprising fluid is a liquid, or a slush of liquid and solids.

2. The labelled methane comprising fluid according to claim 1, wherein the labelled methane comprising fluid comprises 2 to 10 ppm odorant, calculated on the total mass of the labelled methane comprising fluid.

3. The labelled methane comprising fluid according to claim 1, wherein the labelled methane comprising fluid comprises 4 to 6 ppm odorant, calculated on the total mass of the labelled methane comprising fluid.

4. The labelled methane comprising fluid according to claim 1, wherein the carrier is iso-butane.

5. The labelled methane comprising fluid according to claim 1, wherein the odorant is ethyl acrylate or a mixture of ethyl acrylate and ethyl mercaptan.

6. A fuel for automotive industry, marine industry, or for power generation, comprising an odorized methane comprising fluid according to claim 1.

7. The labelled methane comprising fluid according to claim 1, wherein the labelled methane comprising fluid 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.

8. The labelled methane comprising fluid according to claim 7, wherein the odorized methane is at a pressure of from 250 mbara to 76 bara.

9. A process for preparing a labelled methane comprising fluid comprising methyl acetate in a range of from 1 to 250 ppm, the process comprising the following steps: a) adding methyl acetate to a methane comprising liquid, or a methane comprising slush of liquid and solids; b) adding an odorant in a range of from 1 to 100 ppm, and a carrier in a range of from 0.1 to 10 m/m % wherein the odorant and the carrier are added separately and/or mixed, and wherein the methyl acetate is added separately and/or mixed with the odorant and/or the carrier, and wherein the carrier is propane, n-butane, iso-butane, or a mixture of two or more thereof, and wherein the odorant is ethyl acrylate, ethyl mercaptan, or a mixture thereof.

10. The process according to claim 9, comprising the following steps: b1) adding the odorant to the carrier and b2) adding at least a part of the mixture obtained in step b1) to a methane comprising liquid, or a methane comprising slush of liquid and solids, and adding methyl acetate separately and/or mixed with the odorant and the carrier.

11. The process according to claim 9, wherein a stream comprising a tracer and/or the odorant is added to a gas stream, the liquid stream, or the stream of a slush of liquid and solids, using a flow controller or an injection pump and a PLC (programmable logic controller).

12. The process according to claim 9, wherein the liquid or slush comprising methane is at a temperature in a range of from 62 C. to 185 C., and at a pressure in a range of from 20 mbara to 120 bara.

13. The process according to claim 12, wherein the liquid or slush comprising methane is at a pressure in a range of from 250 mbara to 76 bara.

14. A process for preparing a labelled methane comprising fluid comprising methyl acetate in a range of from 1 to 250 ppm, the process comprising the following steps: a) adding methyl acetate to a methane comprising gas; b) adding an odorant in a range of from 1 to 100 ppm of an odorant, and in a range of from 0.1 to 10 m/m % of a carrier to methane comprising gas, wherein the odorant and carrier are added separately and/or mixed, and wherein the methyl acetate is added separately and/or mixed with the odorant and/or the carrier, and wherein the carrier is propane, n-butane, iso-butane, or a mixture of two or more thereof, and wherein the odorant is ethyl acrylate, ethyl mercaptan, or a mixture thereof; and c) liquefying the mixture obtained in step a) to a temperature in a range of from 62 C. to 185 C. and a pressure in a range of from 20 mbara to 120 bara.

15. The process according to claim 14, comprising the following steps: b1) adding the odorant to the carrier, and b2) adding at least a part of the mixture obtained in step b1) to the methane comprising gas, wherein the methane comprising gas preferably is at a temperature in a range of from 40 to +200 C., and adding the methyl acetate separately and/or mixed with the odorant and the carrier, and c) liquefying the mixture obtained in step 2) to a temperature in a range of from 62 C. to 185 C. and a pressure in a range of from 20 mbara to 120 bara.

16. The process according to claim 14, wherein the methane comprising gas is at a temperature in a range of from 25 to +85 C.

17. The process according to claim 14, wherein the pressure in step (b) is in a range from 250 mbara to 76 bara.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) 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.

(2) Labelled Methane Comprising Liquid or Slush

(3) 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.

(4) 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.

(5) 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.

(6) 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.

(7) 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.

(8) 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.

(9) 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.

(10) 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.

(11) 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.

(12) Preferably the carrier is iso-butane.

(13) Preferably the odorant is ethyl acrylate or a mixture of ethyl acrylate and ethyl mercaptan.

(14) Process in which a Tracer is Added to Liquid or Slush

(15) 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.

(16) 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:

(17) 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.

(18) 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: 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,

(19) whereby the odorant and carrier are added separately and/or mixed, and

(20) whereby the methyl acetate is added separately and/or mixed with odorant and/or carrier, and

(21) whereby the carrier is propane, n-butane, iso-butane, or a mixture of two or more thereof, and

(22) whereby the odorant is ethyl acrylate, ethyl mercaptan, or a mixture thereof.

(23) 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.

(24) 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.

(25) 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.

(26) Preferably the carrier is iso-butane.

(27) Preferably the odorant is ethyl acrylate or a mixture of ethyl acrylate and ethyl mercaptan.

(28) Preferably step a) of the process is performed by:

(29) a1) adding odorant to carrier and

(30) 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

(31) adding methyl acetate separately and/or mixed with odorant and carrier.

(32) 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).

(33) Process in which a Tracer is Added to Gas, Followed by Liquefaction

(34) 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.

(35) 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:

(36) 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;

(37) 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.

(38) Preferably step a) is performed as follows:

(39) 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,

(40) whereby the odorant and carrier are added separately and/or mixed, and

(41) whereby the methyl acetate is added separately and/or mixed with odorant and/or carrier, and

(42) 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.

(43) 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.

(44) 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.

(45) 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.

(46) Preferably the carrier is iso-butane.

(47) Preferably the odorant is ethyl acrylate or a mixture of ethyl acrylate and ethyl mercaptan.

(48) Preferably steps a) and b) of the process are performed by:

(49) a1) adding odorant to carrier, and

(50) a2) adding at least a part of the mixture obtained in step a1) to a methane comprising gas,

(51) 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

(52) adding the methyl acetate separately and/or mixed with odorant and carrier, and

(53) 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.

(54) 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).

(55) Use

(56) 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

(57) 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.

(58) The results are summarized in the following tables.

(59) Sample Preparation:

(60) TABLE-US-00001 Concentration Concentration in added to liquid phase natural gas after liquefaction Sample Odorant [ppm] [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

(61) From the sample preparation follows that methyl acetate dissolves well at low temperatures.

(62) It also follows that some odorants do not dissolve well at very low temperatures. They crystallize out.

(63) 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.

(64) Measurements on Labelled or Odorized Natural Gas Using a Gas Cylinder:

(65) TABLE-US-00002 Amount of odorant (using gas detector) Odor at Sample [ppm] 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.

(66) 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.

(67) In the headspace of the cryostat none of the odorants was detected by either gas detection or smelling.

(68) Measurements on Labelled or Odorized LNG in Cryostat:

(69) TABLE-US-00003 Temperature Pressure Odor at Sample of liquid [K] [PSI] 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:

(70) TABLE-US-00004 Boil off gas (using gas Odor at Sample detector) [ppb] 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

(71) 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.