Patent Grant
9726427
This invention concerns a new and efficient process for producing liquid nitrogen.
Liquid nitrogen is normally produced as a by-product of oxygen production. While there are sizable market demands for nitrogen by itself, in fields such as glass making, chemical inverting, electronics, and food preparation, these are end demands for the gas product, and the liquid form is merely a convenience for transportation and storage.
Large or stand alone demands for nitrogen gas are conventionally supplied by nitrogen gas generators, which often involve cryogenic distillation but produce no meaningful amounts of nitrogen in liquid form. When there is a large demand for the liquid form, without the simultaneous requirement of oxygen, nitrogen gas generators are typically coupled with a separate nitrogen liquefaction unit to fulfill this requirement.
It is a major object of the invention to provide an improved process for the direct production of liquid nitrogen, for example as a sole product in an integrated process, saving both power and capital. Basically, the improved process is enabled by use of systems containing distillation columns, operating in series at different pressure levels, to extract a higher yield of nitrogen per unit of compressed air feed processed, as will be seen. The process basically includes:
a) passing a portion of pressurized air feed through a cold expander and feeding a part of the air exhaust from said expander as a gaseous air stream into the bottom of a first column having a top condenser,
b) passing another portion of the pressurized air feed through the main heat exchanger for cooling and liquefying, passing said portion of air through a valve and feeding as a liquid air stream into the middle of the first column;
c) separating the said gaseous and said liquid air streams in the first column into a first liquid nitrogen stream and a first oxygen-enriched liquid stream;
d) feeding the first oxygen-enriched liquid stream into the middle of a second column having a bottom reboiler, in which the liquid is evaporated due to indirect heat exchange with the nitrogen vapor in the first column top condenser, and a top condenser;
e) separating the first oxygen-enriched liquid stream in the second column into a second liquid nitrogen stream and a second oxygen-enriched liquid stream;
f) feeding the second oxygen-enriched liquid stream into the middle of a third column having a bottom reboiler, in which the liquid is evaporated due to indirect heat exchange with the nitrogen vapor in the second column top condenser, and a top condenser, or into an upper reboiler;
g) separating the second oxygen-enriched liquid stream in the third column into a third liquid nitrogen stream and a third oxygen-enriched liquid stream, and feeding the third oxygen-enriched liquid stream into the upper reboiler;
h) evaporating the oxygen-enriched liquid stream in the upper reboiler due to indirect heat exchange with the nitrogen vapor in the third or second column top condenser;
i) removing the first liquid nitrogen stream from the first column and feeding it into the top of the third or second column;
j) removing the second liquid nitrogen stream from the second column and feeding it into the top of the third column or using it as a liquid nitrogen product;
k) removing the third liquid nitrogen stream from the third column and using it as a liquid nitrogen product;
l) removing the evaporated oxygen-enriched stream from the upper reboiler, warming it and removing from the process.
As will be seen, the cleaned and pressurized air feed is split in two streams, the first stream is passed through a warm expander, the second stream is further compressed in boosters by using expander power, previously cooled in a main heat exchanger and split in two portions, one portion of this air feed is passed through a cold expander and the other portion is further cooled and liquefied in the heat exchanger; using a tripe or double distillation columns system to enhance recovery of liquid nitrogen from air enabling substantial reduction in the feed air compressor, and absorber size and power.
A further object is to provide for use of these multiple distillation column systems to enhance recovery of nitrogen from air, and to permit use of an air recycle process to produce refrigeration. Significant reductions in main heat exchanger size and cost are enabled.
Yet another object is provision of a complete process including provision of distillation columns, condenser-reboilers, heat exchangers and compressors, operating as disclosed herein.
Referring to the schematic of
A portion 16 (or all) of the compressed air stream 14 is then boosted in one or two compressors 107 and 109, driven by one or two turbo expanders 112 and 111, to a pressure between 70 and 90 bara at 18. The other portion 15 of the compressed air is fed in the warm turbo expander 111 and then to the heat exchanger 113 at 17.
The boosted air is then cooled in the heat exchanger 113, and a portion is fed at 19 to the cold turbo expander 112, the remainder 23 being further cooled and liquefied, then expanded in a valve 114 and fed to the middle of the first distillation column 115 as a liquid air stream.
The exhaust 20 from the cold turbo expander is split. One portion returns at 21 to provide cooling in the aforementioned heat exchanger 113 while the split remainder to fed at 25 into the bottom of the first distillation column 115 as a gaseous air stream. In that first column, operated about from 7.5 to 9 bara, the air is distilled into pure nitrogen (from 1.0 to 0.0001 mol % of O2) at 26, and condensed in the top condenser 116, a portion of the condensate being removed at 27 as a first liquid nitrogen stream, cooled in the heat exchanger 121 and passed through a valve 122 into the top of the third column 119. The remainder returns at 28 to the first column as reflux.
The bottom liquid in the first column is rich in oxygen (24 to 26% O2). This first oxygen-enriched liquid, removed at 29, is cooled in exchanger 121 and fed through a valve 123 into the middle of the second column (operated from about 5.0 to 6.5 bara), where it joins with liquid descending in this column. This liquid descends countercurrent to the vapor generated by the bottom reboiler 116.
The vapor ascending in the second column is progressively rectified until a pure nitrogen is achieved on the highest rectification stage. This nitrogen stream is condensed in the top condenser 118 and a portion removed at 31 and passed through valve 125 into the top of the third column 119, while the remainder descends as reflux.
The bottom liquid in the second column is richer yet in oxygen (32-33% of O2), removed at 30 as a second oxygen-enriched liquid, throttled at 124 and fed into the middle of the third column 119 (operated at 3-3.6 bara), where it joins with liquid descending in this column. This liquid descends countercurrent to the vapor generated by bottom reboiler 118.
The vapor ascending in the third column is progressively rectified until a pure nitrogen is achieved on the highest rectification stage. This nitrogen stream is condensed in the top condenser 120 and a portion removed at 32 as a liquid nitrogen product while the remainder descends as reflux.
The bottom liquid in the third column is richer yet in oxygen (50-52% of O2), removed at 33 as a third oxygen-enriched liquid, throttled in 126 to about one atmosphere and transferred to the upper reboiler 120.
A very small amount of the oxygen rich (approximately 78% O2) liquid is removed at 34 from the upper reboiler 120 to guard against build up of a dangerous substances in that reboiler as contaminants.
The vapor exiting the upper reboiler (waste) moves through the sub-cooling heat exchanger 121 and enters at 36 the main heat exchanger 113 where the refrigeration is recovered. At the exit of the main exchanger some of the waste is vented, the rest being used at 38 to regenerate the adsorber 104 associated with water and carbon dioxide removal.
The example stream parameters of the process for producing liquid nitrogen at 88.9 K corresponding to the pressure in the third column 3.27 bara are shown in the Table 1. Using the process with the triple column system allows increasing the liquid nitrogen output (LIN) from 0.33 mol/mol of processed air (p.a.) for the existent process to 0.59 mol/mol p.a. (The processed air flow rate is equal to the feed air flow rate). The increase in liquid nitrogen recovery enables a 20% reduction in the specific power and substantial reduction in the feed air compressor and adsorber size and cost.
The liquid nitrogen product can be subcooled in 127 from the temperature about 86-89 K at 32 to the temperature about 79-81 K at 40 by evaporating a part of liquid nitrogen stream 41 in 128 at reduced pressure close to atmospheric. The evaporating a part of liquid air stream at reduced pressure for the preliminary subcooling can be also used.
Referring to the schematic of
A portion 16 (or all) of the compressed air stream 14 is then boosted in one or two compressors 107 and 109, driven by one or two turbo expanders 112 and 111, to a pressure between 55 and 75 bara at 18. The other portion 15 of the compressed air is fed in the warm turbo expander 111 and then in the heat exchanger 113 at 17.
The boosted air is then cooled in the heat exchanger 113, and a portion 19 is fed to the cold turbo expander 112, the remainder 23 being further cooled and liquefied, then expanded in a valve 114 and fed in the middle of the first (lower) distillation column 115 as a liquid air stream.
The exhaust 20 from the cold turbo expander is split. One portion returns at 21 to provide cooling in aforementioned heat exchanger 113 while the split remainder 25 is passed through a throttling valve 119, wherein the pressure is decreased by up to 2 bar (for example, from 6.5 to 4.5 bara), and then at 33 fed into the bottom of the first (lower) column as a gaseous air stream.
In that first (lower) column, operated about from 4.5 to 6.5 bara, the air is distilled into pure nitrogen (from 1.0 to 0.0001 mol % of O2) at 26, and condensed in the top condenser 116, a portion of the condensate being removed at 27, as a first liquid nitrogen stream, cooled in the heat exchanger 121 and passed through a valve 122 into the top of the second (upper) column. The remainder returns at 28 to the lower column as reflux.
The bottom liquid in the lower column is rich in oxygen (27 to 28% O2). This first oxygen-enriched liquid removed at 29 is cooled in 121 and fed through a valve 123 into the middle of the upper column (operated from about 2.7 to 3.3 bara), where it joins with liquid descending in this column. This liquid descends countercurrent to the vapor generated by the bottom reboiler 116.
The vapor ascending in the upper column 117 is progressively rectified until a pure nitrogen is achieved on the highest rectification state. This nitrogen stream is condensed in the top condenser 118 and a portion removed at 32 as a liquid nitrogen product while reminder descends as reflux.
The bottom liquid in the upper column is richer yet in oxygen (43-45% of O2), removed at 30 as a second oxygen-enriched liquid throttled in 124 to about one atmosphere and transferred to the upper reboiler 118.
A very small amount of the oxygen rich (approximately 73% O2) liquid is removed at 34 from the upper reboiler to guard against build up of a dangerous substances in that reboiler as contaminants.
The vapor exiting the upper reboiler (waste) moves through the sub-cooling heat exchanger 121 and enters at 36 the main heat exchanger 113 where the refrigeration is recovered. At the exit of the main exchanger some of the waste is vented, the rest being used at 38 to regenerate the adsorber 104 associated with water and carbon dioxide removal.
The example stream parameters of the process for producing liquid nitrogen an 88.1 K corresponding to the pressure 3.05 bara in the upper column are shown in the Table 2. Using the process with the double column system allows increasing the liquid nitrogen output (LIN) from 0.33 mol/mol of processed air (p.a.) for the existent process to 0.52 mol/mol p.a. The increase in liquid nitrogen recovery enables a 15% reduction in the specific power and substantial reduction in the feed air compressor and adsorber size and cost.
The part of the air exhaust from the cold expander is passed into the lower column through a throttling valve using for the expander exhaust pressure control and allowing also to additional increasing the liquid nitrogen recovery. For example, if the pressure in this valve is decreased by 2 bar (from 6.5 to 4.5 bara), the liquid nitrogen output (LIN) is increased by 0.021 mol/mol p.a., that is 3.8% (0.020/0.522=1.038).
The pressure of the liquid nitrogen product can be increased by using a liquid column. For example, if the difference in elevation between the top of the upper column and the place of withdrawal of the liquid nitrogen product is equal to 16 m, the pressure can be increased by 1.2 bar.
As previously noted, the liquid nitrogen product can be subcooled in 127 from the temperature about 86-89 K at 32 to the temperate about 79-81 K at 40 by evaporating a part of the liquid nitrogen stream 41 at reduced pressure close to atmospheric.
The example conditions of the process with the double column system (
Using the evaporating part of the liquid air stream at reduced pressure for the preliminary subcooling of liquid nitrogen product enables 13% reduction in the specific power as compared with the existent process.
The advantages of the air recycle are lower size (by 33%) of the main heat exchanger as compared with the nitrogen recycle.
The booster compressors 107 and 109 can operate in series as shown in
Feeding the liquid air stream into the lower column allows to increase the LIN output as compared with feeding this stream into the upper column. As is seen from the Table 4, LIN is increased by 4% (0.522/0.502=1.04). In addition, feeding the liquid air stream into the lower column allows reducing of the throttling valve and pipe size.
The liquid air stream fed into the lower column should be equal to at least 40% of the processed air.
The reflux ratio in the columns and correspondingly the number of trays makes a greater impact on the liquid nitrogen product yield and other parameters, that affect the energy and equipment costs. It is estimated that the optimal relationship between the reflux ratio and the minimum reflux ratio for the columns is approximately from 1.1. to 1.2, if the liquid nitrogen product contains about 0.01% of oxygen.
The waste gas removed from the main heat exchanger 113 contains from 38% O2 (Table 3) to 43.4% O2 (Table 2). For the purpose of decreasing the oxygen content in the regeneration gas, one or more trays can be added above the upper reboiler to provide two separate streams: a regeneration gas and a waste stream with increased oxygen content (Table 3).
This method of decreasing the oxygen content in the regeneration gas result in increasing the boiling temperature in the upper reboiler and the pressure in the columns and therefore leads to reducing the liquid nitrogen recovery. Another method in which the pressure in the columns is not increased is discussed below.
Referring to the schematic of
A very small amount of the oxygen rich (approx 80% O2) liquid is removed at 34 from the second upper reboiler 120 to guard against build up of a dangerous substances in that reboiler as contaminants.
As is seen from the Table 5, the oxygen content in the regeneration gas is equal to 25%, that is much less than in case of using one upper reboiler (43.4% O2), Table 2). The temperature difference in the first upper reboiler is equal to 3.74 K and in the second upper reboiler—1.17 K (Table 5), whereas the temperature difference in the case of using one upper reboiler is equal to 1.20 K (Table 2). The total surface of the first and second upper reboiler is less by 17% than the surface in case of using one upper reboiler.
The part 25 of the air exhaust from the cold expander 112 can be passed into the lower column 115 through an additional expander 119 (
a. The bottoms from the columns can be passed to the upper reboiler;
b. The liquid air stream can be fed to either column;
c. The first and second liquid nitrogen stream or the first liquid nitrogen stream can be used as a liquid nitrogen product;
e. The portions of the liquid nitrogen product removing from the distillation columns are passed through throttling valves into a liquid separator, from which the liquid is removed as a liquid nitrogen product at the temperature about 79-81 K and the vapor is passed through heat exchangers and removed from the process.
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