AU2010322827A1

AU2010322827A1 - Process and apparatus for separation of nitrogen from LNG

Info

Publication number: AU2010322827A1
Application number: AU2010322827A
Authority: AU
Inventors: Adrian Finn; Grant Johnson; Terence Tomlinson
Original assignee: Costain Oil Gas and Process Ltd
Current assignee: Costain Oil Gas and Process Ltd
Priority date: 2009-11-30
Filing date: 2010-11-30
Publication date: 2012-06-21
Also published as: EP2507567B1; EP2507567A2; GB2462555A; GB0920947D0; GB2462555B; US20120285196A1; AU2018204827A1; WO2011064605A3; AU2016244250A1; WO2011064605A2

Abstract

The present application is concerned with processes and apparatuses for the separation of nitrogen from liquefied natural gas feeds. The processes comprise the steps of: (i) cooling the feed and passing the feed to a fractionation column; (ii) withdrawing from the fractionation column an overhead vapour stream having an enriched nitrogen content, and a liquid stream having a reduced nitrogen content; (iii) dividing the overhead vapour stream from step (ii) into at least first and second overhead streams; (iv) compressing, cooling and at least partially condensing at least the first overhead stream from step (iii); and (v) expanding the stream from step (iv) and passing the expanded stream to the fractionation column as reflux, and wherein cooling in step (iv) is provided, at least in part, by heat exchange with one or more streams from the fractionation column.

Description

WO 2011/064605 PCT/GB2010/051997 Process and Apparatus for Separation of Nitrogen from LNG This invention relates to processes and apparatus for the separation of nitrogen from liquefied natural gas (LNG) - mixtures comprising nitrogen gas and low-boiling 5 hydrocarbons, such as methane, ethane, propane and butane. Nitrogen is found in many natural gas reservoirs, sometimes at relatively high levels, for example greater than around 5 mol%, which can necessitate removal to meet specifications for use as fuel, but often at lower levels not requiring removal. As high 10 quality gas fields are depleted, natural gas increasingly needs to be sourced from lower quality gas fields, containing higher levels of contaminants such as nitrogen. Many natural gas reservoirs are not sufficiently close to gas consumers to make pipeline transportation economical and infrastructure has grown worldwide for the transportation 15 of gas in liquefied form as LNG. The presence of greater than about 1 mol% nitrogen in LNG, can lead to auto-stratification and rollover in storage tanks, which presents a significant safety concern, and there is therefore a need for efficient techniques for the separation of nitrogen from LNG, even for relatively low nitrogen levels. 20 For relatively low nitrogen levels of approximately 1 to 2 mol%, nitrogen removal from LNG can be achieved by the separation of the nitrogen rich vapour, also referred to as "flash gas", which is evolved when the pressure of sub-cooled LNG is reduced to the LNG storage tank pressure - which is typically just above atmospheric pressure. For feed gas nitrogen levels of greater than about 2 mol% of nitrogen, a fractionation column 25 is typically employed to achieve separation of nitrogen from the LNG, while avoiding excessive flash gas flow rates. Fractionation systems used for the separation of nitrogen from liquefied natural gas typically incorporate a reboiler to produce stripping vapour, required to reduce the 30 nitrogen level in the LNG product to less than 1 mol%.

WO 2011/064605 PCT/GB2010/051997 -2 An example of a conventional apparatus for separation of nitrogen from LNG is shown in Figure 1. 5 A nitrogen-containing LNG feed stream (101) already sub-cooled at elevated pressure is further cooled in a reboil heat exchange system (102). The resultant stream (103) is expanded in a hydraulic expansion turbine (104) to give a two-phase stream (105), which is fed to a fractionation column (106). 10 Liquid (140) from the bottom tray (or packed section) of the fractionation column is partially vaporised in the reboil heat exchange system (102), to produce stripping vapour (141) which is fed to the fractionation column, and thereby also providing refrigeration to further sub-cool the feed stream (101). 15 A LNG stream (107) having low nitrogen content is withdrawn from the bottom of the fractionation column, and is reduced in pressure across a valve (108) to give a two phase stream (109). The two-phase stream (109) is then passed to a vapour-liquid separator (111) to separate a flash gas stream (110) and a low pressure LNG stream (112) for storage. The flash gas stream (110) is passed to a compressor (134), and a 20 resulting compressed stream (135) is cooled by a heat exchanger (136) to give a fuel gas stream (137). An overhead vapour stream (113) rich in nitrogen, but with significant methane content, is withdrawn from the top of the fractionation column (106). 25 While low temperature fractionation processes, such as that shown in Figure 1, allow a LNG product having a low nitrogen content to be obtained, the nitrogen vapour overhead from the fractionation column generally comprises significant amounts of methane as the column incorporates no rectification section. The methane-containing overhead vapour 30 is typically used as fuel gas for power generation or to drive compression equipment. However, restrictions exist as to the nitrogen content of fuel gas which may be used in gas turbines, particularly those derived from aero engines, which can typically burn WO 2011/064605 PCT/GB2010/051997 -3 gases comprising up to 10 mol%, or up to 15 mol% nitrogen, and sometimes as high as 20 mol% nitrogen. Alternatively, the methane-containing overhead vapour from the fractionation column is 5 sometimes used as part of a refrigeration cycle in processes that require methane as a refrigerant. It would be preferable if the methane content of the fractionation overhead vapour could be substantially eliminated. There is therefore a need in the art for efficient separation processes that are able to separate mixtures of nitrogen and LNG to form a natural gas product that is low in nitrogen, and preferably substantially free of nitrogen, 10 and also a nitrogen product that is low in hydrocarbons, and preferably substantially free of hydrocarbons. One solution to the issue of high methane content of the overhead vapour from the fractionation column would be to feed the overhead vapour to a separate nitrogen 15 rejection unit that is able to produce a nitrogen stream with low methane content suitable for venting to the atmosphere and a methane rich stream suitable for use as fuel gas. In addition to compression and heat exchange equipment, this would require additional separation equipment including one or more vapour/liquid separators and fractionation columns. 20 The process and apparatus of the present invention avoids the necessity for a nitrogen rejection unit by producing an overhead vapour stream from the LNG fractionation that has a suitable composition (i.e. substantially devoid of hydrocarbons) for venting to the atmosphere. 25 By recycling a portion of the nitrogen-containing overhead vapour stream from the fractionation column it has surprisingly been found that an improvement in separation may be obtained. More specifically, the recycled portion may be used as a nitrogen-rich reflux stream, which nitrogen-rich reflux stream may be efficiently cooled by heat 30 exchange with one or more streams withdrawn from the fractionation, particularly against evaporating methane rich liquid streams. By avoiding a separate nitrogen rejection unit, thermodynamic losses are reduced and process efficiency is increased, leading to WO 2011/064605 PCT/GB2010/051997 -4 greater LNG production with lower power consumption, as well as improved separation in the fractionation system. The process of this invention also avoids the operating complexity of a separate nitrogen rejection unit and is robust to changes in feed composition. 5 In accordance with the present invention, there is provided a process for the separation of nitrogen from a liquid feed comprising liquefied natural gas and nitrogen, the process comprising the steps of: 10 (i) cooling the feed and passing the feed to a fractionation column; (ii) withdrawing from the fractionation column an overhead vapour stream having an enriched nitrogen content, and a liquid stream having a reduced nitrogen content; (iii) dividing the overhead vapour stream from step (ii) into at least first and 15 second overhead streams; (iv) compressing, cooling and at least partially condensing at least the first overhead stream from step (iii); and (v) expanding the stream from step (iv) and passing the expanded stream to the fractionation column as reflux, 20 wherein cooling in step (iv) is provided, at least in part, by heat exchange with one or more streams from the fractionation column. By recycling a portion of the overhead vapour stream to the fractionation as reflux, the 25 process of the present invention adds a rectification section to the fractionation column, which enables an overhead stream to be obtained from the fractionation column that is substantially devoid of hydrocarbons. For example, the process of the present invention is capable of producing an overhead stream from the fractionation column that comprises less than 2 mol% methane, less than 1 mol% methane, less than 0.5 mol% 30 methane, and potentially as low as 0.1 mol% methane.

WO 2011/064605 PCT/GB2010/051997 -5 Furthermore, by cooling and at least partially condensing the compressed first overhead stream in heat exchange with one or more streams from the fractionation column, the heat integration of the process is improved, thereby reducing energy demands. 5 The proportion of the overhead vapour stream from step (ii) that is recycled to the column as reflux in steps (iii) to (v) is preferably in the range of from 20 to 80 mol% of the total overhead vapour stream, more preferably 30 to 70 mol%, and most preferably 40 to 60 mol% of the total overhead vapour stream from the fractionation column. However, the exact amount of reflux depends on the nitrogen content of the feed and overhead 10 stream purity. An advantage of the present invention is that liquid feeds comprising various quantities of nitrogen can be processed while maintaining methane content of the overhead stream simply by varying the proportion of the overhead vapour stream that is recycled to the column as reflux. 15 As used herein, the expression "one or more streams from the fractionation column" refers to any liquid or gas from the fractionation column that can be used as a source of refrigeration to cool a compressed overhead stream from step (iv). Thus, the expression may refer to overhead vapour withdrawn from the top of the fractionation column. The expression may also refer to the liquid stream withdrawn from the bottom of the 20 fractionation column. The expression may further refer to a side stream obtained from an intermediate stage of the column. Still further, the expression may refer to liquid and/or vapour within the column where one or more heat exchange steps takes place within the column. 25 The LNG feed may consist of, or consist substantially of, methane. The feed may also comprise small amounts of other hydrocarbons such as, for example, ethane, propane, butane and/or heavier hydrocarbons. The hydrocarbons in the LNG feed usually comprise greater than 80 mol% methane, more typically greater than 85 mol% methane, and potentially up to near 100% methane. The balance of the LNG feed may comprise 30 ethane, propane, butane and/or heavier hydrocarbons. Preferably the total content of ethane and/or propane and/or heavier hydrocarbons in the LNG feed is less than 20 mol%, more preferably less than 10 mol%, and most preferably less than 5 mol%. The WO 2011/064605 PCT/GB2010/051997 -6 total content of propane and/or heavier hydrocarbons in the LNG feed is preferably less than 10 mol%, more preferably less than 5 mol%, and most preferably less than 2 mol%. The total content of hydrocarbons heavier than propane in the LNG feed is preferably less than 5 mol%, more preferably less than 2 mol% and most preferably less than 1 5 mol%. The process of the present invention may be used in particular for the separation of nitrogen from LNG feeds that comprise up to 40 mol% nitrogen. For instance, the feed may comprise up to 30 mol% nitrogen, up to 20 mol% nitrogen or up to 15 mol% 10 nitrogen. Preferably, the feed comprises at least 1 mol% nitrogen, for example at least 2 mol% nitrogen, possibly 5 mol% nitrogen, or at least 10 mol% nitrogen. The present invention is particularly applicable to the separation of nitrogen from feeds that comprise or consist of liquefied natural gas. 15 The fractionation column is typically operated in a pressure range of from 100 to 500 kPa, more preferably 100 to 300 kPa, and most preferably 120 to 200 kPa. For example, suitable operating pressures for the fractionation column include 130 kPa, 140 kPa, 150 kPa, 160 kPa, 170 kPa, 180 kPa and 190 kPa. The operating temperature of the 20 fractionation column is dependent on the operating pressure, but the overhead temperature is generally in the range -175 'C to -190 'C and the bottom liquid temperature is generally in the range -135 'C to -160'C. It will be appreciated that, as used herein, expressions such as "an overhead vapour 25 stream having an enriched nitrogen content" or "a liquid stream having a reduced nitrogen content" are intended to refer to the relative nitrogen content of the respective stream when compared with the nitrogen content of the feed. Thus, an overhead vapour stream having an enriched nitrogen content is one that comprises a higher mole fraction of nitrogen than that of the feed. Similarly, a liquid stream having reduced nitrogen 30 content is one that comprises a lower mole fraction of nitrogen than that of the feed.

WO 2011/064605 PCT/GB2010/051997 -7 Generally, the feed is supplied to the fractionation column at or around the operating temperature and pressure of the column. Suitable operating temperatures and pressures for the fractionation column are discussed above. In most cases, the LNG feed will be supplied at a pressure significantly higher than the operating pressure of the 5 fractionation column. For example, a liquefied natural gas feed would typically have a pressure in the range of from 3,000 to 10,000 kPa. In most cases it is therefore necessary to expand the cooled feed to column pressure. For example, the feed may be expanded to column pressure across an expansion valve or by way of an expansion turbine. Expansion turbines have the benefit of extracting work from the process under 10 near-isentropic conditions and reducing the amount of upstream cooling of the feed LNG that is necessary, and thus providing a reduction in energy requirements in upstream liquefaction plant. The cooled and expanded feed is preferably supplied to the fractionation column as a 15 two-phase vapour-liquid mixture. More preferably, the two-phase mixture has a vapour fraction of from 1 to 40 mol%, more preferably 2 to 20 mol%, and most preferably from 3 to 10 mol%, for example 5 to 8 mol%. In one embodiment, cooling in step (iv) is provided, at least in part, by heat exchange 20 with at least a portion of the overhead vapour stream withdrawn from the fractionation column. In a further embodiment, cooling in step (iv) is provided, at least in part, by heat exchange with at least a portion of the liquid product stream withdrawn from the 25 fractionation column. The portion of the liquid product stream passed in heat exchange with the compressed first overhead vapour stream in step (iv) may optionally be expanded first, in order to provide further cooling. Heat to the fractionation column is preferably provided, at least in part by a reboiler. 30 Heated vapour from the reboiler is fed back to the fractionation column to strip nitrogen from the descending LNG in the column.

WO 2011/064605 PCT/GB2010/051997 -8 Where the fractionation column comprises a reboiler, cooling in step (iv) may be provided, at least in part, by heat exchange with a stream from the fractionation column 5 in the reboiler. The type of reboiler that may be used is not limited, and a person of skill in the art can select suitable reboiler systems. For example, thermosyphon, forced-circulation, and kettle reboilers may be used in the process of the invention. The fractionation column 10 may comprise an internal reboiler, located within the column, or an external reboiler located outside the fractionation column. Where an internal reboiler is used, the reboiler is preferably immersed in boiling liquid at the bottom of the fractionation column. Where an external reboiler is used, a liquid 15 stream is withdrawn from the column and fed to the reboiler to produce a heated vapour stream, which is returned to the column as stripping vapour. In preferred embodiments, the bulk of the condensing duty required to cool and at least partially condense the compressed overhead stream from step (iv) is provided by heat 20 exchange with one or more evaporating methane-rich liquids, which may be selected from the liquid product stream withdrawn from the fractionation column and/or boiling liquid at the bottom of the fractionation column and/or a liquid side-stream that is withdrawn from the column and fed to a column-side reboiler. 25 In another embodiment, further cooling of the first overhead stream from step (iii) may be provided by heat exchange with the LNG feed. In another embodiment, heat exchange with a liquid stream from the fractionation column in the reboiler may be used to provide cooling of the feed in step (i). 30 The reflux feed is fed to the top stage of the fractionation column in step (v) to provide rectification of the column vapour, and thereby improve separation, reducing methane WO 2011/064605 PCT/GB2010/051997 -9 content of the column overhead vapour. The reflux stream is expanded before being fed to the fractionation column, for example using an expansion valve or an expansion turbine. 5 The liquid stream withdrawn from the fractionation column in step (ii) is preferably expanded to form a two-phase vapour-liquid stream. As noted above, this expanded stream, or a portion thereof, may be used to provide cooling in step (iv). The two-phase stream is then passed to a vapour-liquid separator to separate a low pressure liquid hydrocarbon stream substantially free of nitrogen, and a hydrocarbon vapour stream. 10 Preferably, the hydrocarbon vapour stream contains less than about 15 mol% nitrogen, and more preferably less than about 10 mol% nitrogen. The hydrocarbon vapour stream may advantageously be compressed and cooled to form a fuel gas product. Alternatively, this stream may be used as part of a refrigeration cycle. 15 In accordance with another aspect of the present invention, there is provided an apparatus for the separation of nitrogen from a feed comprising liquefied natural gas and nitrogen, the apparatus comprising: (i) means for cooling and expanding the feed; 20 (ii) a fractionation column for producing an overhead vapour stream and a bottom liquid stream; (iii) means for conveying the cooled and expanded feed from step (i) to the fractionation column; (iv) means for dividing the overhead vapour stream from the fractionation 25 column into at least first and second overhead streams; (v) means for compressing at least the first overhead stream; (vi) one or more heat exchangers for cooling and at least partially condensing the compressed stream from step (v) in heat exchange with one or more streams from the fractionation column; 30 (vii) means for conveying at least one stream from step (v) to the one or more heat exchangers; and WO 2011/064605 PCT/GB2010/051997 -10 (viii) means for conveying the compressed, cooled and at least partially condensed first overhead stream from step (vi) to an expanding means and from the expanding means to the fractionation column as reflux. 5 In a preferred embodiment, the apparatus of the invention comprises a heat exchanger for cooling and condensing at least one stream from step (v) in heat exchange with at least a portion of the overhead vapour stream withdrawn from the column. In a further preferred embodiment, the apparatus of the invention comprises a heat 10 exchanger for cooling and condensing at least one stream from step (v) in heat exchange with at least a portion of the condensed stream withdrawn from the column. The apparatus may further comprise an expander to expand the condensed stream withdrawn from the column, or a portion thereof, before heat exchange with the at least one stream from step (v). 15 The fractionation column may comprise one or more reboilers, which may be internal or external to the column. The type of reboiler that may be used is not particularly limited, and thermosiphon, forced-circulation, and kettle reboilers are examples of reboiler types that are compatible with the apparatus of the invention. 20 Where the fractionation column comprises a reboiler, the reboiler may be a heat exchanger as specified in step (vi) which is operable to provide cooling and condensing to the at least one stream from step (v) via heat exchange with a stream from the fractionation column. 25 In a further embodiment, the reboiler is operable to provide cooling to the feed via heat exchange with a stream from the fractionation column. The apparatus of the invention preferably comprises means for expanding the bottom 30 liquid stream from step (ii), at least a portion of which may be passed to a heat exchanger in step (vi) as described above, a vapour-liquid separator, and means for conveying the expanded stream to the vapour-liquid separator to separate a liquid WO 2011/064605 PCT/GB2010/051997 - 11 stream and a vapour stream. The apparatus may further comprise means for compressing and cooling a vapour stream withdrawn from the vapour-liquid separator. Suitable means for expanding the stream from step (vi) and optionally the bottom liquid 5 stream from step (ii) include expansion valves and expansion turbines. Suitable operating parameters for the process of the present invention are disclosed in detail above. It is to be understood that the apparatus of the invention is operable in accordance with parameters discussed above in connection with the process of the 10 invention. Furthermore, preferred operating parameters for the process of the invention are also preferred operating parameters for the apparatus of the invention. The invention will now be described in greater detail with reference to preferred 15 embodiments and with the aid of the accompanying figures, in which: Figure 1 shows a conventional fractionation apparatus for the separation of nitrogen from a gaseous mixture comprising nitrogen gas and hydrocarbons, as described above; 20 Figure 2 shows a fractionation apparatus in accordance with the present invention; and Figure 3 shows another embodiment of a fractionation apparatus in accordance with the present invention. 25 In the embodiment of the invention shown in Figure 2, a sub-cooled liquid feed stream (201) comprising LNG and nitrogen is further cooled in reboil heat exchange system (202), to give stream (203). Stream (203) is expanded in hydraulic expansion turbine (204) to give a two-phase stream (205) which is fed to the fractionation column (206). 30 A liquid stream (240) is removed from the bottom tray (or packed section) of the fractionation column below the two-phase feed stream (205) and is partially vaporised to WO 2011/064605 PCT/GB2010/051997 - 12 produce stripping vapour (241) in reboil heat exchange system (202), providing refrigeration to further sub-cool the feed stream (201) and condense nitrogen rich reflux stream (223). 5 Nitrogen rich overhead vapour (213) is removed from the fractionation column (206) and passed to a heat exchange system (214) where it is warmed to a suitable temperature (215) for atmospheric venting (217) downstream of a pressure control valve (216). A portion (218) of the nitrogen rich overhead vapour (213) from the fractionation column 10 is compressed in a compression system (219) to give a compressed stream (220). Compression system (219) includes inter-stage cooling which is not shown. The compressed stream (220) is then cooled (typically in heat exchange against air or water) in a cooler (221) to give a high pressure nitrogen rich stream (222). The high pressure nitrogen rich stream (222) is further cooled in heat exchange systems (214) and (202) to 15 give a liquid stream (224) which is further sub-cooled in the heat exchange system (214) to provide a sub-cooled liquid stream (225). The sub-cooled liquid stream (225) is let down to fractionation column pressure across a valve (226) to give a two phase stream (227) which is supplied as reflux to the 20 fractionation column (206). A LNG stream (207), with low nitrogen content, is removed from the fractionation column (206), and is let down to storage pressure across a valve (208) to give a two-phase stream (209). The two-phase stream (209) is then passed to a vapour-liquid separator 25 (211) and a flash gas stream (210) and a low pressure LNG product stream (212) for storage are obtained. The flash gas stream (210) is compressed using a compressor (234), giving a stream (235), which is cooled (typically in heat exchange against air or water) in a cooler (236) to give a fuel gas stream (237). 30 In this embodiment of the invention, the necessary refrigeration to cool and sub-cool the nitrogen rich reflux stream (222) to form the stream (225) is provided by heat exchange with the overhead vapour (213) from the fractionation column (206) and the liquid stream WO 2011/064605 PCT/GB2010/051997 -13 (240) that is fed to the reboil heat exchange system (202). The embodiment of the invention shown in Figure 3 differs from that of Figure 2 by way of the heat exchange systems that are employed to provide the reflux stream to the 5 fractionation column (306). Thus, a sub-cooled liquid feed stream (301) comprising LNG and nitrogen is further cooled in a reboil heat exchange system (302), to give a stream (303). Stream (303) is expanded in hydraulic expansion turbine (304) to give a two phase stream (305) which is fed to the fractionation column (306). 10 A liquid stream (340) is removed from the bottom tray (or packed section) of the fractionation column (306) below the two-phase feed stream (305) and is partially vaporised to produce stripping vapour (341) in the reboil heat exchange system (302), which provides refrigeration to further sub-cool the feed stream (301). 15 Nitrogen rich overhead vapour (313) from the fractionation column (206) passes to a heat exchange system (314) where it is warmed to a suitable temperature (315) for atmospheric venting (317) downstream of pressure control valve (316). A portion (318) of the nitrogen rich overhead vapour (313) from the fractionation column 20 is compressed in a compression system (319) to give a compressed stream (320). The compression system (319) includes inter-stage cooling which is not shown. The compressed stream (320) is then cooled (typically in heat exchange against air or water) in a cooler (321) to give a high pressure nitrogen rich stream (322). The high pressure nitrogen rich stream (322) is further cooled and sub-cooled in the heat exchange system 25 (314) to provide a sub-cooled liquid stream (325). The sub-cooled liquid stream (325) is let down to fractionation column pressure across a valve (326) to give a two phase stream (327) which is supplied as reflux to the fractionation column (206). 30 A LNG stream (307), with low nitrogen content, is removed from the fractionation column (306). A portion (328) of the stream (307) is let down to just above storage pressure WO 2011/064605 PCT/GB2010/051997 - 14 across a valve (330) to produce a two-phase stream (331), which is vaporised to provide refrigeration in the heat exchange system (314). A remaining portion (329) of the stream (307) is let down to storage pressure across a valve (308) to give a two-phase stream (333). The stream (332) resulting from vaporisation of the stream (331) in the heat 5 exchange system (314) is combined with the stream (333) to give a two-phase stream (309). The two-phase stream (309) is then passed to a vapour-liquid separator (311) to separate a flash gas stream (310) and a low pressure LNG product stream (312) for storage. The flash gas stream (310) is compressed by means of a compressor (334), giving a stream (335), which is cooled (typically in heat exchange against air or water) in 10 a cooler (336) to give a fuel gas stream (337). Examples Example 1 (comparative Example) 15 Table 1 shows operating data for the separation of nitrogen from a LNG feed comprising 10 mol% nitrogen, 85 mol% methane, 4 mol% ethane and 1 mol% propane, at a mass flow rate of 200,000 kg/h, according to the prior art separation system described in Figure 1. Reference is made to the vapour fraction, temperature, pressure, mass flow, 20 and molar composition of specific numbered streams (numbering of streams as in Figure 1).

WO 2011/064605 PCT/GB2010/051997 -15 Table 1 Stream Number (101) (103) (105) Description LNG Feed Expander Inlet LNG to Column Vapour Fraction (molar) 0.000 0.000 0.081 Vapour Liquid Temperature (0C) -141.2 -157.1 -166.7 -166.7 -166.7 Pressure (kPa(a)) 5300 5250 170 170 170 Mass Flow (kg/h) 200000 200000 200000 21281 178719 Molar Flow Methane (kmole/h) 9402 9402 9402 320 9081 Nitrogen (kmole/h) 1106 1106 1106 576 530 Ethane (kmole/h) 442 442 442 0 442 Propane (kmole/h) 111 111 111 0 111 Total (kmole/h) 11061 11061 11061 897 10164 Table 1 (continued) Stream Number (107) (109) (110) Column Description Vapour-Liquid Separator Inlet Flash Gas Bottom Liquid /apour Fraction (molar) 0.000 0.039 Vapour Liquid 1.000 Temperature ('C) -156.3 -161.7 -161.7 -161.7 -161.7 Pressure (kPa(a)) 170 105 105 105 105 Mass Flow (kg/h) 161338 161338 6321 155017 6321 Molar Flow Methane (kmole/h) 8798 8798 330 8469 330 Nitrogen (kmole/h) 72 72 37 35 37 Ethane (kmole/h) 442 442 0 442 0 Propane (kmole/h) 111 111 0 111 0 Total (kmole/h) 9423 9423 366 9056 366 5 WO 2011/064605 PCT/GB2010/051997 -16 Stream Number (112) (113) (135) (137) LNG Column Overhead Compressed Cooled Flash Description Product Vapour Flash Gas Gas /apour Fraction (molar) 0.000 1.000 1.000 1.000 Temperature ('C) -161.7 -167.0 96.0 40.0 Pressure (kPa(a)) 105 160 5050 5000 Mass Flow (kg/h) 155017 38662 6321 6321 Molar Flow Methane (kmole/h) 8469 604 330 330 Nitrogen (kmole/h) 35 1034 37 37 Ethane (kmole/h) 442 0 0 0 Propane (kmole/h) 111 0 0 0 Total (kmole/h) 9056 1638 366 366 It will be noted that the prior art process produces an overhead vapour stream (113) from the fractionation column that comprises a significant amount of methane (37 mol%), and 5 which requires further processing to separate the remaining nitrogen. This is in contrast with the process of the present invention in which the overhead vapour stream (113) is substantially free of methane (see below). Example 2 10 Table 2 shows corresponding operating data for the separation of nitrogen from the LNG feed used in Example 1, at a mass flow rate of 200,000 kg/h, according to the process of the invention as described in Figure 2.

WO 2011/064605 PCT/GB2010/051997 -17 Table 2 Stream Number (201) (203) (205) (207) Description LNG Feed Expander LNG to Column Column Inlet Bottom Liquid Vapour Fraction (molar) 0.000 0.000 0.080 Vapour Liquid 0.000 Temperature (0C) -146.3 -157.1 -166.7 -166.7 -166.7 -156.3 Pressure (kPa(a)) 5300 5250 170 170 170 170 Mass Flow (kg/h) 200000 200000 200000 21117 178883 171064 Molar Flow Methane (kmole/h) 9402 9402 9402 316 9086 9397 Nitrogen (kmole/h) 1106 1106 1106 573 533 76 Ethane (kmole/h) 442 442 442 0 442 442 Propane (kmole/h) 111 111 111 0 111 111 Total (kmole/h) 11061 11061 11061 889 10172 10026 Table 2 (continued) Stream Number (209) (210) (212) (213) DescriptionVapour-Liquid Flash Gas Hydrocarbon Column Separator Inlet Product Overhead Vapour /apour Fraction (molar) 0.039 Vapour Liquid 1.000 0.000 1.000 Temperature ('C) -161.7 -161.7 -161.7 -161.7 -161.7 -190.9 Pressure (kPa(a)) 105 105 105 105 105 160 Mass Flow (kg/h) 171064 6729 164336 6729 164336 67065 Molar Flow Methane (kmole/h) 9397 351 9045 351 9045 12 Nitrogen (kmole/h) 76 39 37 39 37 2387 Ethane (kmole/h) 442 0 442 0 442 0 Propane (kmole/h) 111 0 111 0 111 0 Total (kmole/h) 10026 390 9636 390 9636 2399 WO 2011/064605 PCT/GB2010/051997 -18 Table 2 (continued) Stream Number (217) (218) (222) (223) (224) (225) Nitrogen Cooled Condensed Sub-cooled Nitrogen Nitrogen Description Compressor Nitrogen Nitrogen Nitrogen Suction Recycle Suction Recycle Recycle Recycle Vapour Fraction (molar) 1.000 1.000 1.000 1.000 0.000 0.000 Temperature ('C) 30.0 -73.9 40.0 -154.1 -157.1 -179.0 Pressure (kPa(a)) 101 120 2400 2360 2310 2290 Mass Flow (kg/h) 28936 38129 38129 38129 38129 38129 Molar Flow Methane (kmole/h) 5 7 7 7 7 7 Nitrogen (kmole/h) 1030 1357 1357 1357 1357 1357 Ethane (kmole/h) 0 0 0 0 0 0 Propane (kmole/h) 0 0 0 0 0 0 Total (kmole/h) 1035 1364 1364 1364 1364 1364 Table 2 (continued) Stream Number (227) (235) (237) Nitrogen Recycle Compressed Cooled Flash Column Inlet Flash Gas Gas Vapour Fraction (molar) 0.136 Vapour Liquid 1.000 1.000 Temperature ('C) -191.6 -191.6 -191.6 95.9 40.0 Pressure (kPa(a)) 160 160 160 5050 5000 Mass Flow (kg/h) 38129 5211 32918 6729 6729 Molar Flow Methane (kmole/h) 7 0 7 351 351 Nitrogen (kmole/h) 1357 186 1171 39 39 Ethane (kmole/h) 0 0 0 0 0 Propane (kmole/h) 0 0 0 0 0 Total (kmole/h) 1364 186 1178 390 390 5 It will be noted that the process of the present invention shown in Figure 2 gives rise to a nitrogen rich overhead vapour stream (213) which comprises 99.5 mol% of nitrogen, and WO 2011/064605 PCT/GB2010/051997 -19 only 0.5 mol% methane (in comparison with 63 mol% nitrogen and 37 mol% methane in the overhead stream (213) in Example 1). This is reflected in the amount of hydrocarbon product (212) obtained, which represents 87.1 mol% of the total feed, compared with only 81.9 mol% in Example 1. 5 The improved separation obtained by the process of the present invention can be attributed to the provision of the low temperature nitrogen rich reflux stream (227), which is obtained at -191.6 'C and supplied to the column at a temperature 25 'C below the feed (205) to the column. The rectification of column vapour provided by this nitrogen 10 rich reflux stream allows the temperature differential between the overhead vapour stream (213) and the liquid hydrocarbon stream (207) to be increased to 35.3 'C, and the temperature differential between the nitrogen rich overhead vapour stream (213) and the feed (205) to the column to be increased to 23.3 'C, reflective of the increased purity of the nitrogen rich overhead vapour stream (213). In Example 1, in contrast, where no 15 nitrogen rich reflux stream is provided, the temperature differential between the column overhead vapour stream (213) and the liquid hydrocarbon stream (207) is only 10.3 'C, and the temperature differential between the column overhead vapour stream (213) and the feed (205) to the column is negligible at 0.3 'C, reflective of much poorer separation. 20 Example 3 Table 3 shows corresponding corresponding operating data for the separation of nitrogen from the LNG feed used in Example 1, at a mass flow rate of 200,000 kg/h, 25 according to the process of the invention as described in Figure 3.

WO 2011/064605 PCT/GB2010/051997 -20 Table 3 Stream Number (201) (203) (205) (307) Expander Column Bottom Description LNG Feed LNG to Column Inlet Liquid Vapour Fraction (molar) 0.000 0.000 0.071 Vapour Liquid 0.000 Temperature (0C) -142.5 -159.0 -167.4 -167.4 -167.4 -157.3 Pressure (kPa(a)) 5300 5250 170 170 170 170 Mass Flow (kg/h) 200000 200000 200000 18996 181004 172094 Molar Flow Methane (kmole/h) 9402 9402 9402 263 9139 9397 Nitrogen (kmole/h) 1106 1106 1106 527 579 113 Ethane (kmole/h) 442 442 442 0 442 442 Propane (kmole/h) 111 111 111 0 111 111 Total (kmole/h) 11061 11061 11061 791 10270 10063 Table 3 (continued) Stream Number (309) (310) (312) (313) (317) Vapour-Liquid Flash Hydro- Column nitrogen Description carbon Overhead N en Separator Inlet Gas Vent product Vapour Vapour Fraction (molar) 0.076 Vapour Liquid 1.000 0.000 1.000 1.000 Temperature ('C) -161.7 -161.7 -161.7 -161.7 -161.7 -190.9 30.0 Pressure (kPa(a)) 105 105 105 105 105 160 101 Mass Flow (kg/h) 172094 13265 158829 13265 158830 59873 27906 Molar Flow Methane (kmole/h) 9397 692 8705 692 8705 11 5 Nitrogen (kmole/h) 113 77 36 77 36 2131 993 Ethane (kmole/h) 442 0 442 0 442 0 0 Propane (kmole/h) 111 0 111 0 111 0 0 Total (kmole/h) 10063 769 9294 769 9293 2142 998 WO 2011/064605 PCT/GB2010/051997 -21 Table 3 (continued) Stream Number (318) (322) (325) (327) Nitrogen Sub-cooled Desciptin CmpresorNitrogen Description Compressor cycle Nitrogen Nitrogen Recycle Column Inlet Recycle Suction Recycle Vapour Fraction (molar) 1.000 1.000 0.000 0.120 Vapour Liquid Temperature ('C) -98.4 40.0 -180.5 -191.6 -191.6 -191.6 Pressure (kPa(a)) 120 2150 2090 160 160 160 Mass Flow (kg/h) 31968 31968 31968 31968 3841 28127 Molar Flow Methane (kmole/h) 6 6 6 6 0 6 Nitrogen (kmole/h) 1138 1138 1138 1138 137 1001 Ethane (kmole/h) 0 0 0 0 0 0 Propane (kmole/h) 0 0 0 0 0 0 Total (kmole/h) 1144 1144 1144 1144 137 1007 Table 3 (continued) Stream Number (331) (332) (337) Cooled Description LNG Refrigerant Supply LNG Refrigerant Return Flash Gas Vapour Fraction (molar) 0.024 Vapour Liquid 0.500 Vapour Liquid 1.000 Temperature ('C) -160.6 -160.6 -160.6 -160.1 -160.1 -160.1 40.0 Pressure (kPa(a)) 125 125 125 105 105 105 5000 Mass Flow (kg/h) 15503 396 15107 15503 7390 8113 13265 Molar Flow Methane (kmole/h) 847 18 828 847 443 403 692 Nitrogen (kmole/h) 10 4 6 10 10 0 77 Ethane (kmole/h) 40 0 40 40 0 40 0 Propane (kmole/h) 10 0 10 10 0 10 0 Total (kmole/h) 906 22 884 1364 725 725 769 5 The process of the present invention shown in Figure 3 also gives rise to an nitrogen rich overhead vapour stream (313) which comprises 99.5 mol% of nitrogen, and only 0.5 WO 2011/064605 PCT/GB2010/051997 - 22 mol% methane (in comparison with 63 mol% nitrogen and 37 mol% methane in the overhead stream (313) in Example 1). As in Example 2, the improved separation obtained by the process is attributable to 5 rectification of the column vapour by the low temperature nitrogen rich reflux stream (327), which is obtained at -191.6 'C and supplied to the column at a temperature 24.2 'C below the feed (205) to the column. This in turn, means that the temperature differential between the nitrogen rich overhead vapour stream (313) and the liquid hydrocarbon stream (307) is increased to 33.6 'C, and the temperature differential 10 between the nitrogen rich overhead vapour stream (313) and the feed (205) to the column is increased to 23.5 'C, reflecting the increased purity of the nitrogen rich overhead vapour stream. In this Example, refrigeration to cool the reflux stream (322) is provided by expanding a 15 portion (328) of the liquid hydrocarbon stream (307). As a result, the flash gas flow is higher in this embodiment at 13265 kg/h compared with 6729 kg/h in Example 2, but as the full reboil duty in exchanger (202) is used to sub-cool the feed LNG, the feed temperature from the liquefaction process can be higher, reducing load on the upstream liquefaction refrigeration system. 20 It will additionally be understood that the LNG feed used in the process of the present invention may undergo additional separation and/or conditioning. Examples of such additional processes include one or more of the following: 25 * Separation of vapour formed on expansion of the LNG feed stream. The separated vapour may, in a preferred example, then be introduced as a separate feed to the fractionation column, and more preferably to the fractionation column above the main feed; 30 * Heating a portion of the LNG feed stream and introducing it as a separate feed to the fractionation column, preferably above the main feed. The portion of the stream is preferably heated by way of a well integrated heat exchange operation; WO 2011/064605 PCT/GB2010/051997 -23 Cooling a portion of the LNG feed stream and introducing it as a separate feed to the fractionation column, preferably above the main feed. The portion of the stream is preferably heated by way of a well integrated heat exchange operation. 5 It will also be understood that the fractionation column, as described in the process of the present invention, may additionally comprise or incorporate a side condenser system. In a preferred example, a vapour side draw is taken from an intermediate point, preferably above the main LNG feed to the fractionation column. In the same way that nitrogen rich 10 reflux is generated from the overhead vapour in the embodiments of the invention described above, the vapour side draw is warmed in a heat exchange operation; compressed and cooled; condensed primarily against an evaporating liquid stream rich in methane and sub-cooled against cold vapour in a heat exchange operation; expanded to the fractionation column pressure; and returned to the fractionation column as an 15 intermediate two phase feed. It is believed that the incorporation of a side condenser system reduces the required overhead reflux flow. As the vapour side draw comprises a mixture of methane and nitrogen, it can be condensed against methane rich liquid streams at a lower pressure 20 than can the overhead stream from the fractionation column, which is purer in nitrogen. As a large proportion of the liquid required for rectification can be met by the side condenser system, compression power requirements overall can be reduced.

Claims

1. A process for the separation of nitrogen from a liquefied natural gas feed, the process comprising the steps of: 5 (i) cooling the feed and passing the feed to a fractionation column; (ii) withdrawing from the fractionation column an overhead vapour stream having an enriched nitrogen content, and a liquid stream having a reduced nitrogen content; 10 (iii) dividing the overhead vapour stream from step (ii) into at least first and second overhead streams; (iv) compressing, cooling and at least partially condensing at least the first overhead stream from step (iii); and (v) expanding the stream from step (iv) and passing the expanded stream to the 15 fractionation column as reflux, wherein cooling in step (iv) is provided, at least in part, by heat exchange with one or more streams from the fractionation column. 20

2. A process according to any of the preceding claims, wherein the liquefied natural gas feed comprises from 1 mol% to 40 mol% nitrogen.

3. A process according to any of the preceding claims, wherein cooling in step (iv) is provided, at least in part, by heat exchange with at least a portion of the overhead 25 vapour stream withdrawn from the fractionation column.

4. A process according to any of the preceding claims, wherein cooling in step (iv) is provided, at least in part, by heat exchange with at least a portion of the liquid stream withdrawn from the fractionation column. 30 WO 2011/064605 PCT/GB2010/051997 -25

5. A process according to Claim 4, wherein at least a portion of the condensed stream withdrawn from the fractionation column is expanded before being passed in heat exchange with the compressed first overhead vapour stream. 5

6. A process according to any of the preceding claims, wherein heat to the fractionation column is provided, at least in part, by a reboiler.

7. A process according to Claim 6, wherein cooling in step (iv) is provided, at least in part, by heat exchange with a liquid stream from the fractionation column in the 10 reboiler.

8. A process according to Claim 6 or Claim 7, wherein the reboiler is an internal reboiler located within the fractionation column. 15

9. A process according to Claim 6 or Claim 7, wherein the reboiler is external to the column.

10.A process according to Claim 9, wherein the feed to the reboiler is a stream withdrawn from the bottom of the fractionation column. 20

11. A process according to any of the preceding claims, wherein further cooling of the first overhead stream from step (iii) is provided by heat exchange with the liquefied natural gas feed. 25

12. A process according to any of Claims 7 to 11, wherein cooling in step (i) is provided, at least in part, by heat exchange with a liquid stream from the fractionation column in the reboiler.

13. A process according to any of the preceding claims, wherein the cooled feed in 30 step (i) is expanded to form a two-phase feed to the fractionation column. WO 2011/064605 PCT/GB2010/051997 -26

14. A process according to any of the preceding claims, wherein the cooled and at least partially condensed first overhead stream from step (iv) is expanded before being fed to the fractionation as reflux in step (v). 5

15.A process according to any one of the preceding claims, wherein the reflux stream of step (v) is at a temperature of from 5 to 50 'C below the temperature of the feed to the column in step (i).

16.An apparatus for the separation of nitrogen from a feed comprising liquefied 10 natural gas and nitrogen, the apparatus comprising: (i) means for cooling and expanding the feed; (ii) a fractionation column for producing an overhead vapour stream and a bottom liquid stream; 15 (iii) means for conveying the cooled and expanded feed from step (i) to the fractionation column; (iv) means for dividing the overhead vapour stream from the fractionation column into at least first and second overhead streams; (v) means for compressing at least the first overhead stream; 20 (vi) one or more heat exchangers for cooling and at least partially condensing the compressed stream from step (v) in heat exchange with one or more streams from the fractionation column; (vii) means for conveying at least one stream from step (v) to the one or more heat exchangers; and 25 (viii) means for conveying the compressed, cooled and at least partially condensed first overhead stream from step (vi) to an expanding means and from the expanding means to the fractionation column as reflux. 30