Process for removing hydrogen by cryogenic distillation in the production of high purity nitrogen

Abstract: A process for removing hydrogen by cryogenic distillation in the production of high purity nitrogen, which comprises: a) feeding a compressed, cleaned and dried feed mixture (12) comprising oxygen and nitrogen, which has been cooled to about the dew point thereof, to a first distillation column 13, whereby said nitrogen 16 is extracted at the top of said distillation column as a liquid, and a liquid stream rich is oxygen 17 is extracted at the bottom of said first distillation column; b) extracting a minor fraction of the gas 30 at the top of the first distillation column, the minor fraction containing the lighter impurities; c) expanding said liquid nitrogen at the top of the first distillation column into a second distillation column 14 at an intermediate level, said second distillation column being operated at a pressure sufficiently lower than the pressure of said first distillation column to provide a sufficient temperature difference in a condenser-reboiler located between the first and second distillation columns; d) vaporizing the liquid stream rich is oxygen in the overhead condenser 4 of the second distillation column 14 against the condensing vapor at the top of the second distillation column to form a condensate at the top of the second distillation column, and returning said condensate to the top of the second distillation column as reflux; e) extracting a minor fraction of the gas 31 at the top of the second distillation column containing substantially all lighter impurities; and f) vaporizing the liquid at the bottom of the second distillation column 14 by heat exchange with the condensing gas at the top of the first distillation column 13, and recovering as product a fraction of the liquid 24, a fraction of the vaporized liquid 29 or both, the product containing substantially no lighter air impurities.

Description: The present invention relates to a process for removing hydrogen by cryogenic distillation in the production of high purity nitrogen. In producing nitrogen by cryogenic distillation of atmospheric air or any mixture comprising oxygen and nitrogen, hydrogen contained in atmospheric air is concentrated into the nitrogen product. Hydrogen contamination is undesirable particularly in electronic applications where very pure nitrogen is required. At present, contaminant hydrogen in nitrogen is removed by passing compressed atmospheric feed air through a catalytic bed at a temperature of about 121 to 250°C (250 to 500°F), whereby the hydrogen reacts with oxygen to form water and carbon dioxide which are then removed in a subsequent step either by adsorption or by reversing exchangers. Removal of hydrogen by this method is undesirable, however, due to the expense of the catalyst and the possible poisoning of the catalyst by other impurities present in air, such as sulfur-containing compounds. Furthermore, the catalytic reactor and the equipment associated therewith are very expensive and represent a significant portion of the total required expense. EP-A-0.485.612, citable under Article 54(3) EPC for designated states DE, FR, only, describes a process for producing high purity nitrogen in which liquid nitrogen produced in a main distillation column is distilled in a sub-rectifier. Both the main column and sub-rectifier have a top condenser cooled using liquid from the bottom of the main column. U3-A-4.927.441 relates to a process for producing high purify nitrogen using a standard cycle with few trays added above a reboiler of a single column. No means are provided for removing hydrogen from the nitrogen. Accordingly, it is an object of the present invention to provide a process for removing hydrogen by cryogenic distillation in the production of high purity nitrogen and in particular such a process which avoids the use of a catalytic reactor. It is further an object of this application to provide a process for removing light impurities from a mixture mainly containing a light product, one or more heavier components and a trace of one or more lighter impurities. Version for the following Contracting State: GB According to the present invention, there is provided a process for removing hydrogen by cryogenic distillation in the production of high purity nitrogen, which entails : a) feeding a compressed, cleaned and dried feed mixture comprising oxygen and nitrogen and lighter impurities, which has been cooled to about the dew point thereof, to a first distillation column, whereby said nitrogen is extracted at the top of said distillation column as a a liquid, and a liquid stream rich in oxygen collects at the bottom of said first distillation column ; b) extracting a minor fraction of a gas at the top of the first distillation column, the minor fraction containing the lighter impurities ; c) feeding said liquid nitrogen from the top of the first distillation column into a second distillation column at an intermediate level, said second distillation column being operated at a pressure sufficiently lower than the pressure of said first distillation column to provide a sufficient temperature difference in a condenser-reboiler located between the first and second distillation columns ; d) vaporizing the liquid stream rich in oxygen in an overhead condenser of the second distillation column against the condensing vapor at the top of the second distillation column to form a condensate at the top of the second distillation column, and returning the condensate to the top of the second distillation column as reflux ; e) extracting a minor fraction of the gas at the top of the second distillation column containing substantially all remaining lighter impurities and f) vaporizing the liquid at the bottom of the second distillation column by heat exchange with the condensing gas at the top of the first distillation column, and recovering as nitrogen product a fraction of the liquid, a fraction of the vaporized liquid or both, the nitrogen product containing substantially no lighter impurities. According to the present invention, there is also provided a process for removing a light product, one or more heavier components and a trace of one or more lighter impurities which comprises : a) feeding a mixture mainly comprising the light product, the one or more heavier components and the trace of one or more lighter impurities to a first distillation column such that the one or more heavier components are separated from the light product containing the lighter impurities, whereby the light product is extracted at the top of the first distillation column as a liquid and a liquid stream rich in the one or more heavier components collects at the bottom of the first distillation column ; and wherein the lighter impurities accumulate at the top of the first column, wherein a portion of the lighter impurities are soluble in the light product liquid, and a portion of the lighter impurities remain in a non-condensible vapor fraction stream, said non-condensible vapor fraction stream being removed from the column along with the lighter impurities contained therein ; b) expanding the light product containing some lighter impurities of the first distillation column into a second distillation column at an intermediate level to produce a light product stream and a minor gaseous fraction containing a greater portion of the remaining lighter impurities ; c) expanding the liquid stream rich in the one or more heavier components extracted from the bottom of the first column into an overhead condenser of the second distillation column, where it is vaporized against the condensing gas stream at the top of the second distillation column, the condensate being returned to the top of the second distillation column as reflux ; d) extracting said minor fraction of the gas at the top of the second distillation column ; and e) vaporizing the liquid at the bottom of the second distillation column by heat exchange with the condensing gas at the top of the first distillation column, and recovering as light product a fraction of the liquid, a fraction of the vaporized liquid or both, the product containing substantially no lighter impurities. According to the present invention there is also provided an apparatus for removing lighter impurities including hydrogen according to the features of claim 6 for designated state GB. Version for the following Contracting States: DE, FR According to the present invention, there is provided a process for removing lighter impurities including hydrogen by cryogenic distillation in the production of high purity nitrogen, which comprises : a) feeding a compressed, cleaned and dried feed mixture comprising oxygen and nitrogen and lighter impurities, which has been cooled to about the dew point thereof, to a first distillation column, whereby said nitrogen is extracted at the top of said distillation column as a liquid, and a liquid stream rich in oxygen is extracted at the bottom of said first distillation column ; b) extracting a minor fraction of a gas at the top of the first distillation column, the minor fraction containing part of the lighter impurities ; c) feeding said liquid nitrogen from the top of the first distillation column into a second distillation column at an intermediate level, said second distillation column being operated at a pressure sufficiently lower than the pressure of said first distillation column to provide a sufficient temperature difference in a condenser-reboiler located between the first and second distillation columns ; d) vaporizing the liquid stream rich in oxygen in an overhead condenser of the second distillation column against the condensing vapor at the top of the second distillation column to form a vaporized oxygen-rich stream and to produce a condensate at the top of the second distillation column, and returning said condensate to a second distillation column as reflux ; e) extracting a minor fraction of the gas at the top of the second distillation column containing substantially all remaining lighter impurities ; and f) vaporizing the liquid at the bottom of the second distillation column by heat exchange with the condensing gas at the top of the first distillation column and recovering as product a fraction of the liquid, a fraction of the vaporized liquid or both, the product containing substantially no lighter impurities. According to the invention, there is also provided a process for removing a light product from a mixture mainly comprising a light product, one or more heavier components and a trace of one or more lighter impurities which comprises : a) feeding said mixture mainly comprising the light product, the one or more heavier components and the trace of one or more lighter impurities to a first distillation column such that the one or more heavier components are separated from the light product containing the lighter impurities, whereby the light product is extracted at the top of the first distillation column as a liquid and a liquid stream rich in the one or more heavier components collect at the bottom of the first distillation column ; and wherein the lighter impurities accumulate at the top of the first column, wherein a portion of the lighter impurities are soluble in the light-product liquid, and a portion of the lighter impurities remain in a non-condensible vapor fraction stream, said non-condensible vapor fraction stream being removed from the column along with the lighter impurities contained therein ; b) expanding the light product containing some lighter impurities or the first distillation column into a second distillation column at an intermediate level to produce a light product stream and a minor gaseous fraction containing a greater portion of the remaining lighter impurities ; c) withdrawing and expanding the liquid stream rich in the one or more heavier components extracted from the bottom of the first column into an overhead condenser of a second distillation column, where substantially all the withdrawn liquid stream is vaporized against the condensing gas stream at the top of the second distillation column, the condensate being returned to the top of the second distillation column as reflux ; d) extracting said minor fraction of the gas at the top of the second distillation column ; and e) vaporizing the liquid at the bottom of the second distillation column by heat exchange with the condensing gas at the top of the first distillation column, and recovering as product a fraction of the liquid, a fraction of the vaporized liquid or both, the product containing substantially no lighter impurities. According to the invention, there are also provided apparatuses for removing lighter impurities including hydrogen by cryogenic distillation in the production of high purity nitrogen comprising the features of claim 10 and of claim 14 respectively for the designated states FR and DE. Version for all Contracting States Figure 1 represents a flow sheet for hydrogen removal by cryogenic distillation in the production of high purity nitrogen, where liquid product is extracted at the bottom of the second column as well as the gaseous product. Figure 2 represents a flow sheet for hydrogen removal by cryogenic distillation in the production of high purity nitrogen, where nitrogen recovery is enhanced with a nitrogen cycle. Oxygen-rich liquid in the bottom of the first column is vaporized by indirect heat exchange with a compressed nitrogen cycle which is condensed and expanded at the top of the first column to increase its reflux and reboil. Figure 3 represents a flow sheet for hydrogen removal by cryogenic distillation in the production of high purity nitrogen, where the refrigeration requirement is achieved by expanding a fraction of compressed air in a turbine before being fed to the first distillation column. The nitrogen recovery is enhanced by condensing an air stream in the bottom reboiler of the first distillation column. In accordance with the present invention, a method is provided for removing hydrogen by cryogenic distillation in the production of high purity nitrogen without using a catalytic reactor containing a catalyst. First, compressed air or a feed mixture comprising oxygen and nitrogen which is substantially free of water and carbon dioxide and which has been cooled to about the dew point thereof is fed to the bottom of a first distillation column which is operated at a pressure such that heavy air components are separated from nitrogen. Thereby, nitrogen is produced at the top of the distillation column as a liquid, and a liquid stream rich in oxygen is produced at the bottom of the distillation column. It is preferred that the first distillation column be operated at a pressure of about 4 to 12 bar in order to effectively separate the heavy air components, such as oxygen and argon, from nitrogen. This air normally contains up to about 20 vpm of hydrogen. As already noted, the first distillation column produces at the top a liquid product rich in nitrogen. As used in the present specification, the term "heavy air components" refers to all components of air which have a lower volatility than nitrogen, i.e. its vapor pressure is lower than the vapor pressure of nitrogen at the same temperature. Similarly, the term "light air components" as used in the present specification is intended to include all components of air which have a higher volatility than nitrogen, i.e. its vapor pressure is greater than the vapor pressure of nitrogen at the same temperature. For example, oxygen and argon are examples of heavy air components, and hydrogen and helium are examples or light air components. Then, the liquid nitrogen is expanded at the top of the first distillation column into a second distillation column at an intermediate level, and the second distillation column is operated at a pressure sufficiently lower than the pressure of the first distillation column to provide a sufficient temperature difference in the condenser-reboiler located between the two columns. Thereafter, the liquid stream rich in oxygen is vaporized in the overhead condenser of the second distillation column to form a condensate of a major fraction of the gas at the top of the second distillation column, and then the condensate is returned to the top of the second column as reflux. Finally, a minor fraction of the gas at the top of the second distillation column is extracted, which contains substantially all the light air components, and the liquid at the bottom of the second distillation column is vaporized by heat exchange with the condensing gas at the top of the first distillation column, and a fraction of this vaporized liquid containing substantially no light air components is recovered as product. Generally, the second distillation column may be operated at any pressure lower than the pressure of the first distillation column to provide a sufficient temperature difference in the condenser-reboiler separating the two columns. It is preferred, however, that the second distillation column be at a pressure at least about 0.4 bars lower than the pressure of the first distillation column. It is even more preferred, however, if the second distillation column is at a pressure about 0.6 bar lower than the pressure of the first distillation column. Moreover, as used in the present specification, the phrase containing "substantially all light air components" means that at least 99.99% of all light air components are contained therein. Also, as used in the present specification, the phrase containing "substantially no light air components" means that no more than 0.01% of all light air components are contained therein. The process of the present invention may be practiced with a number of variations, some of which will now be discussed. First, in addition to the general description provided above, liquid product may also be extracted at the bottom of the second distillation column as well as the gaseous product. This is represented in Figures 2 and 3. Alternatively, a subcooler can be added to subcool the bottom liquid of the first distillation column against the outgoing gaseous product and the residual stream rich in oxygen. This is represented in Figure 2. Furthermore, the refrigeration requirement can be achieved by expanding the stream rich in oxygen, or expanding the gaseous nitrogen product or by adding liquid to the process in a liquid assist or by expanding a fraction of the feed air. The present invention may be used in conjunction with other processes whenever the removal of a light product from a mixture containing heavier components is required. The present invention may also be used advantageously in conjunction with any process where light products are to be removed from mixtures of heavier components. As a specific example, the present process may be used to remove carbon monoxide from mixtures also containing heavier hydrocarbons, such as methane (CH 4 ). Generally, the process is applicable to several hydrocarbon mixtures containing lighter impurities. The present invention may be used with any of these to effect removal of the light component. Beyond petrochemical processes, there are many other types of reaction mixtures which contain a lighter component and one or more heavy components. In some of the processes, the light component in the reaction mixture may be an unreacted raw material. In other processes, the lighter component in the reaction mixture may be one of the reaction products. The present process may be used to advantage with any of these processes to remove light components. Generally, it is preferred, however, to use the present process in conjunction with processes producing a light product from a mixture containing mainly the light product, one or more heavier components and with traces of a lighter impurity. It is more preferred if the lighter impurity is present in the mixture only in an amount of up to about 1% by volume, most preferably only up to about 0.5% by volume. Notably the lighter impurities are accumulated at the top of the first column. Some of the lighter impurities are soluble in the light-product liquid, and some of the lighter impurities remain in a vapor fraction called the non-condensible stream. This stream is removed from the column along with the lighter impurities contained therein. Thus, the present invention provides an efficient means for separating a light product, one or more heavier components and one or more lighter impurities. As noted above, generally, the one or more lighter impurities are present in an amount of up to about 1% by volume, preferably not more than about 0.5% by volume. Generally, as used herein the term "light product" means the mixture component having the higher volatility. The term "heavier components" means the mixture component or components having the lowest volatility. The term "lighter impurities means the impurity component or components having an intermediate volatility and which are present in amounts of only up to about 1% by volume. The "trace" of lighter impurities is intended to mean a minor amount of generally less than 1% by volume. Also, the term "non-condensible" is intended to mean non-condensible under conditions prevailing outlet for the top condenser of both columns. In order to more fully describe the present invention, reference will now be made to Figures 1-3. In Figure 1, a cooled, compressed, cleaned and dried feed stream containing light product, one or more heavier components and a trace of one or more lighter impurities, such as atmospheric air, is fed via conduit (10) to heat exchange means (11), and then to the high pressure column (13) via conduit (12). A nitrogen-rich liquid is fed from the high pressure column (13) to the low pressure column (14) via conduit (16) for feed. Also, liquid nitrogen (LIN) may be removed from the column as liquid product from the bottom of the low pressure column (14). Non-condensible material is withdrawn from the column at condenser-reboiler (15), and from the overhead condenser (80) of the low pressure column. Waste gas is removed from the overhead condenser (80) via conduits (21) and (22), optionally through subcooler (18), to heat exchange means (11), where it exits the process via conduit (28). This waste originates from a bottom stream (17) withdrawn from the high pressure column, wherein after it is optionally passed through subcooler (18) and to the overhead condenser (80) via conduit (20). In Figure 2, a cooled, compressed, cleaned and dried feed stream containing light product, one or more heavier components and a trace of one or more lighter impurities, such as atmospheric air, and which is close to the dew point is fed to an intermediate location of a high pressure column (13), wherein an oxygen-rich stream separates at the bottom and a nitrogen-rich stream at the top. A liquid nitrogen stream is extracted at the top of the high pressure column (13) and fed to the low pressure column (14) via conduit (16) at an intermediate location. A minor gaseous fraction or non-condensible containing some lighter impurities is removed at the top of the high pressure columns (13) via conduit (30). Then, lighter impurities are removed via the non-condensible stream at the top of the low pressure column (14) with the bottom fraction being substantially free, i.e., less than about 0.5% by volume thereof, of lighter impurities. Nitrogen product can be extracted from the bottom of the low pressure column as a liquid (LIN) via conduit (24). Gaseous nitrogen product is extracted from the column via conduit (19) and rewarmed in exchanger (11). A portion of this product is recovered via conduit (54) and the remaining portion is compressed in compressor (60). A fraction of this compressed stream may be recovered as product via conduit (57). The remaining fraction is sent to the high pressure column reboiler (52) via conduit (51) where it condenses to provide the reboil for the high pressure column. Then, the condensed recycle stream is fed via conduit (53) from the reboiler to the top of the high pressure column to provide extra reflux for the high pressure column. An oxygen-rich stream is passed from the bottom of the high pressure column (13) via conduit (17) to the overhead condenser (80) of the low pressure column, whereby it vaporizes and passes to the exchanger (11), and is rewarmed. The rewarmed stream is then fed to an expander and then to an exchanger where it is used to provide required refrigeration and then exits as waste. In Figure 3, fraction of a cooled, compressed, cleaned and dried feed stream is fed via conduit (73) to the bottom reboiler (52) of the distillation column (13) where it is liquified, the liquified feed stream is then fed to the high pressure column (13). Another fraction of the cooled, compressed, cleaned and dried feed stream is expanded via expander (71) into the high pressure column (13), wherein in the top section thereof pure nitrogen and lighter impurities are extracted and in the bottom section oxygen-rich liquid is extracted. Some lighter impurities may be removed via conduit (30). Liquid nitrogen fraction is extracted at the top of the high pressure column and fed via conduit (16) to an intermediate stage of the low pressure column. The gaseous nitrogen fraction which forms at the top of the high pressure column is condensed in reboiler (15) to provide reboil for the low pressure column. The low pressure column (14) further purifies liquid nitrogen feed and a liquid product may be recovered at the bottom of the low pressure column via conduit (24), which is free of lighter impurities. Conduit (19) affords recovery of gaseous nitrogen which is free of lighter impurities. The remaining lighter impurities are removed via conduit (31) and exit at the top of the low pressure column. Oxygen-rich liquid from the bottom of the high pressure column is transferred via conduit (17) to the top condenser (80) of the low pressure column, where it is vaporized and leaves the process via conduit (21), (22) and (28), optionally passing through subcooler (18), and then passing through exchanger (11) Gaseous nitrogen exits the column via conduit (19), optionally passing through the subcooler (18), through conduit (23) and then passing through exchanger (11), wherein after it exits the process via conduit (29). By vaporizing the oxygen-rich liquid, some of the gaseous nitrogen at the top of the low pressure column is condensed and returned as reflux in the low pressure column.

Claims: Claims for the following Contracting State : GB Process for removing lighter impurities including hydrogen by cryogenic distillation in the production of high purity nitrogen, which comprises: a) feeding a compressed, cleaned and dried feed mixture comprising oxygen, nitrogen and lighter impurities, which has been cooled to about the dew point thereof, to a first distillation column (13), whereby said nitrogen is extracted at the top of said distillation column as a liquid, and a liquid stream rich in oxygen is extracted at the bottom of said first distillation column (13); b) extracting a minor fraction (30) of a gas at the top of the first distillation column, the minor fraction containing part of the lighter impurities; c) feeding said liquid nitrogen from the top of the first distillation column into a second distillation column (14) at an intermediate level, said second distillation column being operated at a pressure sufficiently lower than the pressure of said first distillation column to provide a sufficient temperature difference in a condenser-reboiler (15) located between the first and second distillation columns; d) vaporizing the liquid stream rich in oxygen in an overhead condenser (80) of the second distillation column (14) against the condensing vapor at the top of the second distillation column to form a condensate at the top of the second distillation column, and returning said condensate to the top of the second distillation column as reflux; e) extracting a minor fraction (31) of the gas at the top of the second distillation column (14) containing substantially all remaining lighter impurities; and f) vaporizing the liquid at the bottom of the second distillation column (14) by heat exchange with the condensing gas at the top of the first distillation column (13), and recovering as nitrogen product, a fraction of the liquid, a fraction of the vaporized liquid or both, the nitrogen product containing substantially no lighter impurities. A process according to Claim 1, wherein said second distillation column (14) is operated at a pressure at least 0.4 bar below the pressure of said first distillation column (13). A process according to one of Claims 1 or 2, wherein said first distillation column (13) is operated at a pressure of about 4 to 12 bars. A process according to one of Claims 1 to 3, wherein said second distillation column (14) is operated at a pressure of about 0.6 bar below the pressure of said first distillation column (13). A process for removing a light product, one or more heavier components and a trace of one or more lighter impurities which comprises: a) feeding a mixture mainly comprising the light product, the one or more heavier components and the trace of one or more lighter impurities to a first distillation column (13) such that the one or more heavier components are separated from the light product containing the lighter impurities, whereby the light product is extracted at the top of the first distillation column (13) as a liquid and a liquid stream rich in the one or more heavier components collects at the bottom of the first distillation column (13); and wherein the lighter impurities accumulate at the top of the first column, wherein a portion of the lighter impurities are soluble in the light product liquid, and a portion of the lighter impurities remain in a non-condensible vapor fraction stream, said non-condensible vapor fraction stream (30) being removed from the top of the column along with the lighter impurities contained therein; b) expanding the light liquid product containing some lighter impurities of the first distillation column into a second distillation column (14) at an intermediate level to produce a light product stream and a minor gaseous fraction containing a greater portion of the remaining lighter impurities; c) expanding the liquid stream rich in the one or more heavier components extracted from the bottom of the first column into an overhead condenser (80) of the second distillation column, where it is vaporized against the condensing gas stream at the top of the second distillation column, the condensate being returned to the top of the second distillation (14) column as reflux; d) extracting a minor fraction (31) of the gas at the top of the second distillation column; and e) vaporizing the liquid at the bottom of the second distillation column (14) by heat exchange with the condensing gas at the top of the first distillation column (13), and recovering as light product a fraction of the liquid, a fraction of the vaporized liquid or both, the product containing substantially no lighter impurities; An apparatus for removing lighter impurities including hydrogen by cryogenic distillation in the production of high purity nitrogen comprising a double fractionating means including a high pressure fractionating means (13) and a low pressure fractionating means (14), means for providing a fluid connection between the high pressure fractionating means and a feed stream comprising oxygen and nitrogen, means (16) for sending a liquid nitrogen stream from the high pressure fractionating means to an intermediate level of the low pressure fractionating means (16) for further purification, means (17,20) for sending oxygen-enriched liquid from the bottom of the high pressure fractionating means (13) to a condenser (80) at the top of the low pressure fractionating means, means (30, 31) for extracting minor fractions of gas from the top of the high and low pressure fractionating means containing lighter impurity components, means (15) for vaporizing liquid at the bottom of the low pressure fractionating means by heat exchange with gas from the top of the high pressure fractionating means and means for removing a product nitrogen stream from the low pressure fractionating means. An apparatus according to Claim 6, which further comprises a compressed nitrogen cycle in fluid connection with a bottom reboiler (52) of the high pressure fractionating means (13), whereby oxygen-rich liquid in the bottom of the high pressure fractionating means in contact with said reboiler is vaporized by indirect heat exchange, said compressed nitrogen cycle stream being condensed and expanded at the top of the high pressure fractionating means to increase its reflux and reboil. An apparatus according to one of Claims 6 or 7, which further comprises a turbine (71) in fluid connection with said high pressure fractionating means, whereby required refrigeration is achieved by expanding a fraction of the compressed air in said turbine before being fed to the high pressure fractionating means (13). An apparatus according to Claim 8, when dependent on Claim 6, which comprises a bottom reboiler (52) of the high pressure fractionating means (13) wherein the compressed feed stream is condensed against a vaporizing oxygen-rich liquid by indirect heat exchange, and means (74) for feeding condensed feed stream to the high pressure fractionating means. An apparatus according to Claim 6 comprising means for sending vaporized liquid from the condenser (80) to an expansion turbine (27). Claims for the following Contracting States : FR, DE Process for removing lighter impurities including hydrogen by cryogenic distillation in the production of high purity nitrogen, which comprises: a) feeding a compressed, cleaned and dried feed mixture comprising oxygen, nitrogen and lighter impurities, which has been cooled to about the dew point thereof, to a first distillation column (13), whereby said nitrogen is extracted at the top of said distillation column as a liquid, and a liquid stream rich in oxygen is extracted at the bottom of said first distillation column (13); b) extracting a minor fraction (30) of a gas at the top of the first distillation column, the minor fraction containing part of the lighter impurities; c) feeding said liquid nitrogen from the top of the first distillation column (13) into a second distillation column (14) at an intermediate level, said second distillation column being operated at a pressure sufficiently lower than the pressure of said first distillation column to provide a sufficient temperature difference in a condenser-reboiler (15) located between the first and second distillation columns; d) vaporizing the liquid stream rich in oxygen in an overhead condenser (80) of the second distillation column (14) against the condensing vapor at the top of the second distillation column to form a vaporized oxygen-rich stream and to produce a condensate at the top of the second distillation column, and returning said condensate to the top of the second distillation column as reflux; e) extracting a minor fraction (31) of the gas at the top of the second distillation column (14) containing substantially all remaining lighter impurities; and f) vaporizing the liquid at the bottom of the second distillation column (14) by heat exchange with the condensing gas at the top of the first distillation column (13), and recovering as nitrogen product, a fraction of the liquid, a fraction of the vaporized liquid or both, the nitrogen product containing substantially no lighter impurities. A process according to Claim 1, wherein said second distillation column (14) is operated at a pressure at least 0.4 bar below the pressure of said first distillation column (13). A process according to one of Claims 1 or 2, wherein said first distillation column (13) is operated at a pressure of about 4 to 12 bars. A process according to one of Claims 1 to 3, wherein said second distillation column (14) is operated at a pressure of about 0.6 bar below the pressure of said first distillation column (13). A process according to any preceding claim comprising expanding the vaporized oxygen-rich stream in an expander (27) to provide refrigeration for the process. A process according to any preceding claim comprising condensing a gaseous stream of air or nitrogen in a condenser-reboiler (52) at the base of said first distillation column (13). A process for removing a light product from a mixture mainly comprising a light product, one or more heavier components and a trace of one or more lighter impurities which comprises : a) feeding said mixture mainly comprising the light product, the one or more heavier components and the trace of one or more lighter impurities to a first distillation column (13) such that the one or more heavier components are separated from the light product containing the lighter impurities, whereby the light product is extracted at the top of the first distillation column (13) as a liquid and a liquid stream rich in the one or more heavier components collects at the bottom of the first distillation column; and wherein the lighter impurities accumulate at the top of the first column, wherein a portion of the lighter impurities are soluble in the light product liquid, and a portion of the lighter impurities remain in a non-condensible vapor fraction stream (30), said non-condensible vapor fraction stream being removed from the column along with the lighter impurities contained therein; b) expanding the light liquid product containing some lighter impurities of the first distillation column into a second distillation column (14) at an intermediate level to produce a light product stream and a minor gaseous fraction containing a greater portion of the remaining lighter impurities; c) withdrawing and expanding the liquid stream rich in the one or more heavier components extracted from the bottom of the first column (13) into an overheat condenser (80) of the second distillation column (14), where the withdrawn liquid stream is vaporized against the condensing gas stream at the top of the second distillation column, the condensate being returned to the top of the second distillation column as reflux; d) extracting a minor fraction (31) of the gas at the top of the second distillation column (14); and e) vaporizing the liquid at the bottom of the second distillation column (14) by heat exchange with the condensing gas at the top of the first distillation column (13), and recovering as product a fraction of the liquid, a fraction of the vaporized liquid or both, the product containing substantially no lighter impurities. An apparatus according to Claim 7 comprising expanding the vaporized liquid stram in an expander (27) to provide refrigeration for the process. A process according to Claim 6 or 7 comprising condensing a gaseous stream of feed mixture or light product in a condenser reboiler (52) at the bas of the first distillation column (13). An apparatus for removing lighter impurities including hydrogen by cryogenic distillation in the production of high purity nitrogen which comprises a double fractionating means having a high pressure fractionating means (13) in fluid connection with a feed stream comprising oxygen, nitrogen and lighter impurities from which is extracted a first fraction of nitrogen in liquid form, separate conduit means (16) for feeding said liquid nitrogen fraction from the top of said high pressure fractionating means (13) to a low pressure fractionating means (14) for further purification, a bottom reboiler (52) for condensing a gaseous stream by indirect heat exchange with vaporizing oxygen-rich liquid, means for removing lighter impurities including hydrogen from the top of said low pressure fractionating means and the top of the said high pressure fractionating means, and means (74) for feeding said condensed stream from said reboiler (52) to said high pressure fractionating means (13). An apparatus according to Claim 10, wherein said apparatus further comprises a compressed nitrogen cycle in fluid connection with said bottom reboiler (52) of the high pressure fractionating means (13), whereby oxygen-rich liquid in the bottom of said high pressure of fractionating means (13) in contact with said reboiler (52) is vaporized by indirect heat exchange, said gaseous stream being compressed nitrogen. An apparatus according to Claim 10, wherein said gaseous stream is said feed stream. An apparatus according to any of Claims 10 to 12, which further comprises a turbine (71) in fluid connection with said high pressure fractionating means (13), whereby required refrigeration is achieved by expanding a fraction of feed stream in said turbine (71) before being fed to the heat pressure fractionating means (13). An apparatus for removing lighter impurities including hydrogen by cryogenic distillation in the production of high purity nitrogen, which comprises a double fractionating means having a high pressure fractionating means (13) and a low pressure fractionating means (14), said high pressure fractionating means being in fluid connection with a feed stream comprising oxygen, nitrogen and lighter impurities from the top of which is extracted a first fraction of liquid nitrogen, separate conduit means (16) for feeding said liquid nitrogen fraction from the top of said high pressure fractionating means (13) to a low pressure fractionating means (14) for further purification, means (17, 20) for removing liquid crude oxygen from the base of said high pressure fractionating means (13), means (17, 20) for sending all said removed liquid crude oxygen to a condenser (80) at the top of said low pressure fractionating means (14), means for removing lighter impurities from the top of said low pressure fractionating means and the top of said high pressure fractionating means, and means (80) for vaporizing said liquid crude oxygen in said condenser (80) at the top of the said low pressure fractionating means. An apparatus according to Claim 14 including means for sending a fraction of said feed stream to a turbine (71) for expansion and means for sending said expanded feed stream to a high pressure fractionating means (13). An apparatus according to Claim 14 comprising an expander (27) for expanding vaporized liquid crude oxygen from said condenser (80) at the top of said low pressure fractionating means (14).

Inventors: HA BAO, PETRIE WILFRID, VENET FRANCOIS, HA, BAO, PETRIE, WILFRID, VENET, FRANCOIS, Venet, François
Applicants: AIR LIQUIDE, LIQUID AIR ENG CORP, L'AIR LIQUIDE, SOCIETE ANONYME POUR L'ETUDE ET L'EXPLOITATION DES PROCEDES GEORGES CLAUDE, LIQUID AIR ENGINEERING CORPORATION
Application year: 1992
Main classification: F25J3
IPC codes: C01B21, F25J3