EP0783031B1 - Procédé de déshydratation, de désacidification et de dégazolinage d'un gaz naturel, utilisant un mélange de solvants - Google Patents
Procédé de déshydratation, de désacidification et de dégazolinage d'un gaz naturel, utilisant un mélange de solvants Download PDFInfo
- Publication number
- EP0783031B1 EP0783031B1 EP96402909A EP96402909A EP0783031B1 EP 0783031 B1 EP0783031 B1 EP 0783031B1 EP 96402909 A EP96402909 A EP 96402909A EP 96402909 A EP96402909 A EP 96402909A EP 0783031 B1 EP0783031 B1 EP 0783031B1
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- methanol
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- 239000002904 solvent Substances 0.000 title claims description 104
- 239000000203 mixture Substances 0.000 title claims description 97
- 238000000034 method Methods 0.000 title claims description 35
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 20
- 239000003345 natural gas Substances 0.000 title claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 303
- 239000007789 gas Substances 0.000 claims description 119
- 239000002253 acid Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000012071 phase Substances 0.000 claims description 25
- 230000008929 regeneration Effects 0.000 claims description 23
- 238000011069 regeneration method Methods 0.000 claims description 23
- 239000008346 aqueous phase Substances 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 150000004677 hydrates Chemical class 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- 239000012809 cooling fluid Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 239000011877 solvent mixture Substances 0.000 description 28
- 239000007791 liquid phase Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000005057 refrigeration Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 235000021183 entrée Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- 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
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
-
- 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
Definitions
- the invention relates to a method for dehydration and / or gas degassing natural, using a mixture of solvents.
- the treatment of a natural gas requires dehydration, degassing, when natural gas contains condensable hydrocarbons and the deacidification of this gas when the proportion of acid gases it contains is too high.
- the present invention also makes it possible to recover the methanol contained in the gas by a simple and economical way.
- the heavy solvent can for example be a polar solvent such as dimethylformamide (DMF), N-methylpyrrolidone (NMP) or dimethyl sulfoxide (DMSO).
- the heavy solvent can also be a chemical solvent such as example a secondary or tertiary amine, for example hydroxylated.
- methanol makes it possible in particular to very significantly reduce the level of solvent for relatively large contents of acid gases in the gas to be treated.
- the presence of methanol also makes it possible to absorb and separate from the gas to be treated impurities such as, for example, mercaptans, carbonyl sulfide (COS) and carbon disulfide (CS 2 ).
- the gas to be treated arrives via line 1. It contains for example methane, ethane, propane, butane, as well as heavier hydrocarbons, water and acid gases such as for example H 2 S and CO 2 .
- a fraction of this gas is sent through line 2 to the contact column C1, in which it is brought into counter-current contact with a solution of methanol in water arriving via line 3.
- the via line 40 an aqueous phase substantially free of methanol.
- a gas loaded with methanol is recovered via line 4 which is mixed with the gas which has not passed through column C1.
- Gas as well obtained is the gas loaded with methanol from step (a).
- This gas is then sent by line 6 in column C2, in which it is contacted with a mixture of solvents, including methanol, water and a more solvent heavy than methanol, which arrives via line 7.
- This mixture of solvents emerges by the conduit 8 charged with acid gases, while the gas evacuated at the head of the column through line 9 is at least partially rid of the acid gases it contains at entry in column C2 (step (b)).
- the mixture of solvents from this step (b) is first expanded to a intermediate pressure through the expansion valve V1 releasing a phase gas which contains at least some of the hydrocarbons that may have been coabsorbed in the solvent mixture.
- the gas phase and the liquid phase thus obtained are separated in flask B1.
- the additional flow rate of aqueous phase thus provided can be controlled for example to a level of solvent mixture in a recipe or storage tank located for example at the output of column D1.
- the gas phase is evacuated at the head of the balloon B1.
- the residual solvent mixture is evacuated through line 10 and passes into the exchanger E1, in which it is warmed up. It is then expanded through the valve V2 and regenerated in the column distillation D1.
- This column is cooled at the head, which makes it possible to evacuate by the conduit 11 of the acid gases relatively little loaded with solvent and heated in bottom, which allows a mixture of solvents to be discharged through line 12 substantially free of acid gases.
- the acid gases evacuated by the conduit 11 undergo additional refrigeration in the exchanger E5, to recover at least partially the residual methanol.
- the liquid phase thus obtained is collected in the separator flask B20, which also receives back-up from aqueous phase arriving via line 42 and passing through the expansion valve V40.
- the liquid phase thus collected in the separator flask B20 is recycled by the pump P12 through the conduit 43 at the head of the column C2.
- the mixture of solvents discharged through line 12 is taken up by pump P1 and sent through exchanger E1, in which it is cooled by heating the mixture of solvents which arrives via the conduit 10. It is then cooled in the exchanger E2 by exchange with water or cooling air and recycled to column C2.
- step (b) which is evacuated through line 9 receives a top-up methanol arriving via line 13. It is then cooled, first by exchange internally in the E3 exchanger, then by exchange with a refrigeration fluid external from a refrigeration circuit, in the exchanger E4. This refrigeration condenses a methanol solution and a phase liquid hydrocarbon.
- the gas phase thus obtained constitutes the treated gas which is substantially free of water, acid gases and hydrocarbons heavy it contains at the start.
- the three-phase mixture obtained is separated in the balloon B2.
- the treated gas passes through the exchanger E3, in which it is heated in cooling the gas arriving from column C2 and it is evacuated through line 14.
- the liquid hydrocarbon phase obtained is discharged through line 15 and the fraction of the aqueous phase containing methanol obtained which is not removed by the conduit 42 is recycled by pump P2 through conduit 41 to column C1.
- the mixture of solvents sent via line 7 comprises methanol, water and a heavier solvent than methanol.
- the methanol content of the gas discharged through line 9 must be sufficiently high to prevent the formation of ice and / or hydrates during the stage refrigeration, the addition of methanol arriving through line 13 being reduced and intended to compensate for losses. This means that this methanol content is the higher the refrigeration temperature at the outlet of the exchanger E4 is low.
- the methanol content in the solvent mixture arriving through the conduit 7 is also higher as the temperature at which the gas is refrigerated is low.
- the methanol content can be easily regulated by the addition of methanol arriving via line 13.
- the make-up quantity is for example controlled the methanol content in the aqueous phase collected in the separator B2 so as to reach the content required to avoid the formation of hydrates.
- the methanol content in the solvent mixture can be in this case for example between 5 and 50% in molar fraction.
- the heavy solvent which enters into the composition of the mixture of solvents can be a polar solvent such as for example DMF, NMP, DMSO, as described upper; it can also be, sulfolane, propylene carbonate, an alcohol heavier than methanol, an ether or a ketone.
- a polar solvent such as for example DMF, NMP, DMSO, as described upper; it can also be, sulfolane, propylene carbonate, an alcohol heavier than methanol, an ether or a ketone.
- the main condition to respect is that its boiling point is higher than the temperature methanol boiling point and preferably above the boiling point some water. It is also necessary that this solvent is at least partially miscible with water and methanol.
- the heavy solvent content in the solvent mixture may be in this case for example between 10 and 60% in molar fraction.
- the water content forms the complement but it is preferably at least equal at 10% in molar fraction.
- the heavy solvent which enters into the composition of the mixture of solvents can be also a chemical type solvent such as for example a secondary amine or tertiary, generally hydroxylated, chosen for example from monoethanolamine, diethanolamine, diglycolamine, diisopropanolamine, methyldiethanolamine.
- a chemical type solvent such as for example a secondary amine or tertiary, generally hydroxylated, chosen for example from monoethanolamine, diethanolamine, diglycolamine, diisopropanolamine, methyldiethanolamine.
- the amine content in the mixture of solvents can be understood for example between 1 and 10% in molar fraction.
- the heavy solvent is selected according to the specifications required for the treated gas. If selective deacidification is sought, consisting in eliminating H 2 S much more selectively than CO 2 , a selective amine such as for example methyldiethanolamine will be used.
- additives known to a person skilled in the art, such as for example additives making it possible to activate the absorption of CO 2 , or additives acting as corrosion inhibitors, or else additives acting as anti-foaming agents. It may also be advantageous to filter the mixture of solvents which is sent to column C2, in order to stop the solid particles which can promote foaming.
- step (d) allows an aqueous phase to be removed from the bottom of said column substantially free of methanol. This allows you to recover and easily recycle methanol and avoid any pollution linked to the presence of methanol in the released aqueous phase.
- the contact column used can be of different types known to those skilled in the art. the art: with trays or with filling. In the case of a packed column, it can be advantageous to use structured packing.
- the other columns used in the process can be of different known types skilled in the art: with trays or with padding and in particular with padding structure.
- composition of natural gas is for example the following (in kg / h): Water 60.55 Nitrogen 782.37 Carbon dioxide 8770.15 Methane 31,699.87 Ethane 5210.67 Propane 3,088.88 Isobutane 625.43 N-butane 1024.58 Isopentane 330.39 N-pentane 297.37 N-hexane 118.29 N-heptane 343.99 Total 52352.54
- the gas to be treated arrives through line 1 at a temperature of 30 ° C and at a pressure of 70 bars with a flow rate substantially equal to 52352 kg / h.
- a fraction of this gas (50%) is injected into the contact column C1 through line 2.
- a solution containing 65% by mass of methanol in water, at a flow rate of 159 kg / h and at a temperature of 30 ° C, is injected against the current into column C1 by the line 3.
- a phase is eliminated through line 40 aqueous containing 12 ppm mass of methanol at a flow rate of 60 kg / h.
- the gas loaded with methanol is evacuated via line 4 and mixed with gas which has not passed through column C1 and which arrives via line 5.
- the gas thus obtained is sent via line 6 to column C2.
- a solution containing 20% by mass of methanol and 20% by mass of diethanolamine in water is injected against the current into column C2 through line 7 at temperature 40 ° C with a flow rate of 117409 kg / h.
- the mixture of solvents loaded with carbon dioxide is recovered through line 8 to the temperature of 46 ° C.
- the gas evacuated at the head of column C2 via line 9 now contains only 1.8 % mass of carbon dioxide.
- This gas is cooled in the E3 exchangers and E4 at a temperature of -26 ° C.
- the three-phase mixture obtained is separated in the balloon B2.
- the treated gas, discharged through line 14, has a flow rate of 44,889 kg / h.
- the liquid hydrocarbon phase obtained is discharged through line 15.
- the phase aqueous containing methanol is partially recycled in column C1 by conduit 41, the other part (75%) being sent to balloon B20.
- the solvent mixture loaded with carbon dioxide is expanded to a pressure 10 bar via the expansion valve V1, then sent to the separation tank B1.
- the liquid phase from balloon B1 is sent through line 10 into the exchanger E1, where it is heated to a temperature of 60 ° C.
- she is expanded to a pressure of 1.5 bar and injected into the distillation column D1.
- This column is cooled at the head to a temperature of 40 ° C. and heated at the bottom.
- the mixture of solvents recovered by line 12 at a temperature of approximately 80 ° C is taken up by the pump P1, then is cooled in the exchangers E1 and E2 before being recycled in column C2.
- the gas evacuated at the head of column D1 via line 11 is cooled to -26 ° C after its passage through the E5 exchanger.
- Balloon B20 allows a phase to be separated liquid containing mainly methanol and water and a gas phase essentially containing carbon dioxide.
- the aqueous phase is recycled in column C2 via line 43.
- the gas phase is evacuated through the conduit 23.
- step (b) it can be advantageous to optimize the performance of the process, to perform step (b) by putting the gas successively in contact with fractions of mixtures of solvents of compositions different. If a fraction of the mixture is sent at the top and another in a intermediate point, it is advantageous to send a fraction of the mixture of solvents relatively poor in methanol and send to an intermediate point a fraction of the solvent mixture relatively rich in methanol.
- the gas loaded with methanol arrives via line 6 in column C2. He is everything first brought into contact in a first zone (lower part) of the column C2 with a fraction of solvent mixture relatively rich in methanol introduced through conduit 16.
- the methanol content in this first fraction of mixture of solvents can be for example between 20 and 70% in fraction molar.
- the gas is then brought into contact in a second zone (upper part) of column C2 with a fraction of the solvent mixture relatively low in methanol introduced via line 7.
- the methanol content in this second fraction of the solvent mixture can be for example between 5 and 30% in molar fraction. This methanol content must be all the higher as the methanol content in the gas leaving via line 9 is high, that is to say the higher the lower the temperature at the outlet of the exchanger E4, this to avoid the formation of ice and / or hydrates.
- step (b) The mixture of solvents from step (b), that is to say in the case of the example described in relation to FIG. 2a leaving column C2 by the line 8, is regenerated by expansion then by heating in a column of counter-current contact D1, the solvent phase taken from the bottom of said column forming the fraction of the solvent mixture relatively poor in methanol which is injected at the head of the contact column used during step (b), that is to say column C2 in the case of the example described in relation to FIG. 2a.
- the mixture of solvents charged with acid gases exiting through the conduit 8 is first expanded to an intermediate pressure level through the valve V1, releasing a gaseous phase which contains at least part of the hydrocarbons which could be coabsorbed in the solvent mixture.
- This gas phase can be washed with a fraction of a mixture of solvents relatively poor in methanol, the flow rate of which is controlled by the distribution valve V30 and which is sent via line 17 at the head of a counter-current contact section located in column element C10.
- the gas which leaves the head of the column element C10 is thus substantially freed from the acid gases which it contained and can for example serve as fuel-gas or else be recompressed and mixed with the treated gas.
- step (b) it is possible to subject the mixture of solvents from step (b) a first step of expansion at an intermediate pressure to release at least part of the hydrocarbons coabsorbed.
- step (c) it is also possible to wash the gas fraction from the expansion at an intermediate pressure of the mixture of solvents from step (b), by a fraction of the mixture of solvents relatively poor in methanol collected at the bottom of the regeneration column used during step (c).
- the mixture of solvents is expanded to again to a low pressure, for example a pressure close to the atmospheric pressure, through the expansion valve V20.
- the liquid-vapor mixture thus obtained is separated in the separator flask B10.
- the vapor phase formed essentially of acid gases and methane is evacuated through the conduit 18.
- the liquid phase thus obtained is split into two fractions.
- a first fraction, preferably the largest in flow, is taken up by the pump P11 at through conduit 20 and forms most of the mixing fraction of solvents relatively rich in methanol which is sent via line 16 in one intermediate point of column C2.
- a second fraction of the solvent mixture obtained at the outlet of the flask separator B10 is heated in the exchanger E1, by heat exchange with the mixture of solvents from the bottom of column D1, then sent to the distillation column D1.
- Steam reflux is generated at the bottom of column D1 by means of reboiler R1 and a liquid reflux is generated at the top of the column D1 by means of the condenser E6.
- the gas phase resulting from partial condensation in E6 and which is evacuated at the head via line 19 is formed essentially of acid gases and methanol.
- the gas mixture thus obtained is refrigerated in the exchanger E5.
- the liquid-vapor mixture thus obtained is separated in the separator flask B20.
- a make-up of aqueous phase feeds the flask B20 through the conduit 42 and through the expansion valve V40.
- the gas phase formed essentially separate acid gases are evacuated through line 23.
- the liquid phase rich in methanol is taken up by pump P12 through line 22 and, after mixing with the fraction arriving via line 20, forms the fraction of solvent mixture which is sent to an intermediate point in column C2.
- the liquid phase discharged at the bottom of column D1 is taken up by pump P10. It is cooled in the exchanger E1, from which it emerges through the conduit 21. It is then divided into two fractions by means of the distribution valve V30. A first fraction, the largest in flow is cooled in the exchanger E2 by water or cooling air and sent to the top of column C2 by the conduit 7. A second fraction is sent via conduit 17 at the head of column element C10.
- the gas to be treated contains a large proportion of CO 2 and of H 2 S, it may be desirable to obtain separate fractions of acid gases, respectively rich in CO 2 and in H 2 S.
- the gaseous fraction relatively rich in CO 2 which is obtained after the expansion of the mixture of solvents through the expansion valve V20 is sent to the column element C11, in which it is brought into contact with a part a mixture of solvents relatively poor in methanol arriving via line 21, to selectively eliminate the H 2 S present in the gas.
- the mixture of solvents arriving via line 21 is divided into two fractions by passage through the distribution valve V40. A first fraction is sent through the conduit 24 at the head of the column element C11. A second fraction is sent via line 25 to the head of column C2.
- the mixture of solvents collected at the bottom of the column element C11 and arriving by the pump P11 and the line 20 is mixed with the liquid fraction arriving by the line 22.
- the resulting mixture of solvents is sent to an intermediate point of the column C2.
- the gaseous fractions discharged through the conduits 18 and 19 respectively constituting the fractions rich in CO 2 and in H 2 S are not mixed and can undergo separately a complementary treatment, for example by refrigeration, to eliminate at least in part methanol entrained with acid gases.
- Another arrangement that can be used is, instead of refrigerating directly the acid gases arriving through line 18, through line 19 or after mixture of these two fractions, to send these acid gases into an element of rectification column according to the example of arrangement of FIG. 4.
- Acid gases containing methanol obtained by mixing the fractions gas arriving through lines 18 and 19 are sent to the column element C20.
- the gas fraction at the top of the column element C20 is refrigerated in the E5 exchanger.
- the liquid-vapor mixture thus obtained is separated in the flask BR reflux.
- the gas phase rich in acid gases is evacuated through the pipe 23.
- the liquid phase is sent as reflux to the top of the column element C20.
- a liquid phase rich in methanol which is taken up by pump P12 and sent through line 22.
- step (a) it is also possible to at least partially remove the methanol entrained in acid gases by washing these acid gases with water from step (a), that is to say in the embodiments described in relation to FIGS. 1 and 2, collected at the bottom of column C1, the aqueous phase containing methanol thus obtained being returned to step (a), that is to say in the examples of embodiment described in relation to Figures 1 and 2 at the top of column C1.
- a first fraction is expanded through valve V42 and sent to the head of column D1.
- a second fraction is expanded through the valve V41, then is reheated in the exchanger E12 by heat exchange with the mixture fraction of relatively rich solvents do methanol which is taken from a point in below the feed point and sent by the P20 pump in the exchanger E12 from which it emerges through conduit 20, to form at least partially the fraction solvent mixture which is sent to an intermediate point in the column C2.
- the third fraction is expanded through the valve V40, then is reheated in the exchanger E11 by heat exchange with the mixture fraction of solvents relatively poor in methanol which is collected at the bottom of the column regeneration D1 and sent by pump P10 in the heat exchanger E11, from which it emerges through conduit 21, to form at least partially the fraction solvent mixture which is sent to the top of column C2.
- This embodiment of the method is therefore characterized in that the fraction of the solvent mixture relatively rich in methanol which is sent to a point intermediate of the contact column used during step (b) is removed at an intermediate point in the regeneration column used during the step (vs).
- each of these fractions can be sent to several different levels. Of even it is possible to use more than two fractions of different compositions, said fractions being taken from different points in the column of D1 regeneration used during step (c) and sent to points different from the absorption column C2 used during step (b).
- the solvent mixture fraction (s) from the column regeneration D1 are cooled down to a temperature close to the temperature at which step (b) is carried out by heat exchange with one or more fractions of the solvent mixture from step (b) and optionally by an exchange additional thermal, with a cooling fluid such as water or air.
- the absorption step (b) is carried out in column C2 at a temperature by example between +10 and +40 ° C, but it is also possible to reduce the solvent level to operate this step at lower temperatures, with a mixture of solvents selected so as not to become too viscous at these levels of temperature.
- the pressure at which the absorption step is carried out in column C2 can be between a few bars and more than a hundred bars. It can be for example close to 70 bars.
- step (c) natural gas can be refrigerated to a temperature for example between 0 and -100 ° C, the methanol content in the fraction of mixture of solvents sent to the top of the contact column used during step (b) being adjusted so as to obtain in the gas issuing from step (b) a methanol content to avoid the formation of hydrates at the temperature lower obtained during step (c).
- step (c) When the gas contains condensable hydrocarbons, the refrigeration carried out during step (c) allows to degasoline this gas and to adjust the dew point hydrocarbons at the value required for the transport of gas.
- This refrigeration can also make it possible to fractionate this gas by separating by example the LPG present in the gas. It is possible in this case to use all devices known to those skilled in the art, such as for example columns of distillation or heat exchangers operating with liquid reflux.
- the regeneration of the mixture of solvents from step (b) can be carried out after expansion at least in part in a device operating in fractionation and in simultaneous heat exchange.
- the EC1 device can be for example a heat exchanger placed vertically and operating against the current.
- the mixture of solvents arriving from the separator tank B10 is sent to the head of this exchanger. It is heated gradually going down into the exchanger, which causes the formation a gas phase containing mainly acid gases and methanol which is evacuated at the head by the conduit 19, by circulating in the exchanger EC1 at counter-current of the liquid phase constituted by the mixture of solvents.
- the solvent mixture thus leaves purified at the bottom of the exchanger EC1. He is taken back by pump P13, heated in the exchanger E10 and cooled by passing through the exchanger EC1 in which it heats the mixture which descends. At the exit of exchanger EC1, the purified solvent mixture is sent via line 21 in head of the absorption column C2 used during step (b).
- the EC1 exchanger can be, for example, with tubes and shell or even with plates, either brazed aluminum or stainless steel.
- the regeneration step can be carried out in two or more columns operating under different pressure and temperature conditions. It is thus possible, for example, to obtain fractions of acid gases of different compositions, for example a fraction concentrated in CO 2 and a fraction concentrated in H 2 S.
- Each of these regeneration operations can be carried out in one or several distillation sections, some of which can be carried out with a simultaneous heat exchange.
- the regeneration step (c) thus comprises at least two successive regeneration operations, a gaseous fraction rich in CO 2 being obtained at the end of the first operation and a gaseous fraction rich in H 2 S being obtained at the end of the second operation.
- the process also makes it possible to separate impurities such as mercaptans, COS and CS 2 which can, for example, be eliminated with the gaseous fraction rich in H 2 S.
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Gas Separation By Absorption (AREA)
- Drying Of Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9515626 | 1995-12-28 | ||
FR9515626A FR2743083B1 (fr) | 1995-12-28 | 1995-12-28 | Procede de deshydratation, de desacidification et de degazolinage d'un gaz naturel, utilisant un melange de solvants |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0783031A1 EP0783031A1 (fr) | 1997-07-09 |
EP0783031B1 true EP0783031B1 (fr) | 2001-09-26 |
Family
ID=9486064
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96402909A Expired - Lifetime EP0783031B1 (fr) | 1995-12-28 | 1996-12-27 | Procédé de déshydratation, de désacidification et de dégazolinage d'un gaz naturel, utilisant un mélange de solvants |
Country Status (8)
Country | Link |
---|---|
US (1) | US5782958A (no) |
EP (1) | EP0783031B1 (no) |
JP (1) | JP4264594B2 (no) |
CA (1) | CA2194083C (no) |
DE (1) | DE69615522T2 (no) |
DK (1) | DK0783031T3 (no) |
FR (1) | FR2743083B1 (no) |
NO (1) | NO314901B1 (no) |
Families Citing this family (32)
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GB9702742D0 (en) * | 1997-02-11 | 1997-04-02 | Ici Plc | Gas absorption |
FR2760653B1 (fr) * | 1997-03-13 | 1999-04-30 | Inst Francais Du Petrole | Procede de desacidification avec production de gaz acides en phase liquide |
FR2771020B1 (fr) * | 1997-11-19 | 1999-12-31 | Inst Francais Du Petrole | Dispositif et methode de traitement d'un fluide par compression diphasique et fractionnement |
US6183540B1 (en) * | 1999-08-27 | 2001-02-06 | Kinder Morgan, Inc. | Method and apparatus for removing aromatic hydrocarbons from a gas stream prior to an amine-based gas sweetening process |
FR2814379B1 (fr) * | 2000-09-26 | 2002-11-01 | Inst Francais Du Petrole | Procede de desacidification d'un gaz par absorption dans un solvant avec un controle de la temperature |
FR2820430B1 (fr) | 2001-02-02 | 2003-10-31 | Inst Francais Du Petrole | Procede de desacidification d'un gaz avec lavage des hydrocarbures desorbes lors de la regeneration du solvant |
FR2822839B1 (fr) * | 2001-03-29 | 2003-05-16 | Inst Francais Du Petrole | Procede ameliore des deshydratation et de degazolinage d'un gaz naturel humide |
FR2822838B1 (fr) * | 2001-03-29 | 2005-02-04 | Inst Francais Du Petrole | Procede de deshydratation et de fractionnement d'un gaz naturel basse pression |
CA2383283C (fr) * | 2001-05-11 | 2010-09-07 | Institut Francais Du Petrole | Procede de pretraitement d'un gaz naturel contenant des composes acides |
FR2845392B1 (fr) * | 2002-10-07 | 2006-05-26 | Inst Francais Du Petrole | Procede de desacidification d'un gaz naturel |
ITMI20022709A1 (it) * | 2002-12-20 | 2004-06-21 | Enitecnologie Spa | Procedimento per la rimozione dell'idrogeno solforato contenuto nel gas naturale. |
MY136353A (en) * | 2003-02-10 | 2008-09-30 | Shell Int Research | Removing natural gas liquids from a gaseous natural gas stream |
DE10324694A1 (de) * | 2003-05-28 | 2004-12-23 | Uhde Gmbh | Verfahren zur Entfernung von Sauergasen aus unter Druck befindlichem, mit Sauergasverbindungen verunreinigtem Erdgas und Gewinnung der entfernten Sauergase auf erhöhtem Druckniveau |
EP2402068B2 (en) * | 2004-01-20 | 2016-11-16 | Fluor Technologies Corporation | Methods and configurations for acid gas enrichment |
FR2866345B1 (fr) | 2004-02-13 | 2006-04-14 | Inst Francais Du Petrole | Procede de traitement d'un gaz naturel avec extraction du solvant contenu dans le gaz naturel purifie |
WO2007104800A1 (de) † | 2006-03-16 | 2007-09-20 | Basf Se | Verfahren zum inkontaktbringen zweier phasen, deren kontakt von wärmeentwicklung begleitet ist |
US20080256977A1 (en) * | 2007-04-20 | 2008-10-23 | Mowrey Earle R | Hydrocarbon recovery and light product purity when processing gases with physical solvents |
FR2934172B1 (fr) * | 2008-07-28 | 2011-10-28 | Inst Francais Du Petrole | Solution absorbante a base de n,n,n'n'-tetramethylhexane -1,6-diamine et procede d'elimination de composes acides d'un effluent gazeux |
CA2772479C (en) | 2012-03-21 | 2020-01-07 | Mackenzie Millar | Temperature controlled method to liquefy gas and a production plant using the method. |
CA2790961C (en) | 2012-05-11 | 2019-09-03 | Jose Lourenco | A method to recover lpg and condensates from refineries fuel gas streams. |
BR112015012045B1 (pt) * | 2012-11-26 | 2020-11-17 | Equinor Energy As | método e sistema para desidratação de uma fase gasosa e inibição de hidrato de uma fase de hidrocarboneto líquido |
CA2798057C (en) | 2012-12-04 | 2019-11-26 | Mackenzie Millar | A method to produce lng at gas pressure letdown stations in natural gas transmission pipeline systems |
CA2813260C (en) | 2013-04-15 | 2021-07-06 | Mackenzie Millar | A method to produce lng |
JP2015202484A (ja) * | 2014-04-16 | 2015-11-16 | 千代田化工建設株式会社 | 天然ガスの液化システム及び液化方法 |
CA2958091C (en) | 2014-08-15 | 2021-05-18 | 1304338 Alberta Ltd. | A method of removing carbon dioxide during liquid natural gas production from natural gas at gas pressure letdown stations |
RU2587175C2 (ru) * | 2014-11-18 | 2016-06-20 | Общество с ограниченной ответственностью "Газпром добыча Уренгой" | Способ подготовки углеводородного газа к транспорту |
CA2997628C (en) * | 2015-09-16 | 2022-10-25 | 1304342 Alberta Ltd. | A method of preparing natural gas at a gas pressure reduction stations to produce liquid natural gas (lng) |
CN106560505A (zh) * | 2015-09-25 | 2017-04-12 | 新地能源工程技术有限公司 | 一种依靠低温甲醇溶液脱除合成天然气中水的工艺及装置 |
RU2636499C1 (ru) * | 2017-01-19 | 2017-11-23 | Общество с ограниченной ответственностью "Газпром добыча Уренгой" | Способ сбора и подготовки углеводородного газа к транспорту |
RU2736714C1 (ru) * | 2017-03-03 | 2020-11-19 | Дау Глоубл Текнолоджиз Ллк | Способ отделения сероводорода от газовых смесей с использованием гибридной смеси растворителей |
EP3476459B1 (de) * | 2017-10-24 | 2020-10-14 | L'air Liquide, Société Anonyme Pour L'Étude Et L'exploitation Des Procédés Georges Claude | Anlage und verfahren zur abtrennung von schwefelhaltigen komponenten aus beladenem methanol |
CN107916151B (zh) * | 2017-12-30 | 2023-10-20 | 西安长庆科技工程有限责任公司 | 一种用于天然气的脱水系统及方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1669328C3 (de) * | 1967-04-15 | 1974-07-25 | Linde Ag, 6200 Wiesbaden | Verfahren zum Entfernen von sauren Komponenten aus Erdgas |
US3899312A (en) * | 1969-08-21 | 1975-08-12 | Linde Ag | Extraction of odorizing sulfur compounds from natural gas and reodorization therewith |
DE3000250A1 (de) * | 1980-01-05 | 1981-07-16 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zum entfernen von h(pfeil abwaerts)2(pfeil abwaerts)s, co(pfeil abwaerts)2(pfeil abwaerts), cos und merkaptanen aus gasen durch absorption |
FR2550956B1 (fr) * | 1983-08-26 | 1985-10-25 | Petroles Cie Francaise | Procede de purification d'un gaz naturel, pouvant notamment etre integre dans un procede de liquefaction de ce gaz naturel |
DE3505590A1 (de) * | 1985-02-18 | 1986-08-21 | Linde Ag, 6200 Wiesbaden | Verfahren und vorrichtung zum abtrennen unerwuenschter komponenten aus gasgemischen |
US4617038A (en) * | 1985-07-26 | 1986-10-14 | El Paso Hydrocarbons Company | Process for using preferential physical solvents for selective processing of hydrocarbon gas streams |
US4675035A (en) * | 1986-02-24 | 1987-06-23 | Apffel Fred P | Carbon dioxide absorption methanol process |
FR2600554B1 (fr) * | 1986-06-30 | 1988-09-02 | Elf Aquitaine | Procede et dispositif pour la desacidification d'un gaz renfermant h2s ou/et co2 ainsi que des mercaptans |
DE3828227A1 (de) * | 1988-08-19 | 1990-02-22 | Basf Ag | Verfahren zum entfernen von co(pfeil abwaerts)2(pfeil abwaerts) und gegebenenfalls h(pfeil abwaerts)2(pfeil abwaerts) aus gasen |
FR2641542B1 (fr) * | 1988-11-15 | 1994-06-24 | Elf Aquitaine | Procede de decarbonatation et de degazolinage simultanes d'un melange gazeux constitue principalement d'hydrocarbures consistant en methane et hydrocarbures en c2 et plus et renfermant egalement co2 |
-
1995
- 1995-12-28 FR FR9515626A patent/FR2743083B1/fr not_active Expired - Fee Related
-
1996
- 1996-12-27 EP EP96402909A patent/EP0783031B1/fr not_active Expired - Lifetime
- 1996-12-27 DE DE69615522T patent/DE69615522T2/de not_active Expired - Fee Related
- 1996-12-27 CA CA002194083A patent/CA2194083C/fr not_active Expired - Fee Related
- 1996-12-27 DK DK96402909T patent/DK0783031T3/da active
- 1996-12-27 JP JP34925596A patent/JP4264594B2/ja not_active Expired - Fee Related
- 1996-12-27 NO NO19965609A patent/NO314901B1/no not_active IP Right Cessation
- 1996-12-30 US US08/777,442 patent/US5782958A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
DK0783031T3 (da) | 2001-11-26 |
NO965609L (no) | 1997-06-30 |
DE69615522D1 (de) | 2001-10-31 |
DE69615522T2 (de) | 2002-04-25 |
JP4264594B2 (ja) | 2009-05-20 |
NO314901B1 (no) | 2003-06-10 |
FR2743083B1 (fr) | 1998-01-30 |
US5782958A (en) | 1998-07-21 |
FR2743083A1 (fr) | 1997-07-04 |
EP0783031A1 (fr) | 1997-07-09 |
CA2194083C (fr) | 2006-06-06 |
JPH09194851A (ja) | 1997-07-29 |
NO965609D0 (no) | 1996-12-27 |
CA2194083A1 (fr) | 1997-06-29 |
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