The invention relates to a method for producing compressed nitrogen and liquid nitrogen by cryogenic separation of air.
The production of air products in the liquid or gaseous state by cryogenic separation of air in air separation plants is known. Such air separation plants have distillation column systems which can for example take the form of two-column systems, in particular conventional Linde two-column systems, but also three- or multi-column systems. It is also possible to provide apparatus for obtaining other air components, in particular the noble gases krypton, xenon and/or argon (cf. for example F. G. Kerry. Industrial Gas Handbook: Gas Separation and Purification, Boca. Raton: CRC Press, 2006; chapter 3: Air Separation Technology). The distillation column system of the invention can be designed as a conventional two-column system, but also as a three- or multi-column system. In addition to the columns for nitrogen-oxygen separation, it can also have other apparatus for obtaining other air components, for example for obtaining impure, pure or high-purity oxygen or noble gases.
A “main heat exchanger” serves for cooling feed air in indirect heat exchange with recirculation streams from the distillation column system. It can be formed of a single or a plurality of operatively connected, parallel- and/or series-connected heat exchanger sections, for example of one or more plate heat exchanger blocks.
The expression “condenser-evaporator” refers to a heat exchanger in which a first, condensing fluid stream enters into indirect heat exchange with a second, evaporating fluid stream. Each condenser-evaporator has a condensing space and an evaporating space, which consist of condensing passages and, respectively, evaporating passages. The condensation (liquefaction) of the first fluid stream takes place in the condensing space, and the evaporation of the second fluid stream takes place in the evaporating space. The evaporation and condensing spaces are formed by groups of passages which are in a heat-exchanging inter-relationship. The evaporating space of a condenser-evaporator can be designed as a bath evaporator, a falling film evaporator or a forced-flow evaporator.
An “expansion machine” can have any construction. Here, use is preferably made of turbines (turboexpanders).
Conventional two-column methods have just a single condenser-evaporator, the main condenser, and are operated at relatively low pressure, namely just above atmospheric pressure at the top of the low-pressure column. If large quantities of compressed nitrogen are to be obtained, use is made of a modified two-column method, which is operated at higher pressure. This makes it possible to use a low-pressure-column top condenser, and to cool this using an oxygen-rich residual fraction from the distillation column system. Such a method is known from U.S. Pat. No. 4,453,957.
Hitherto, methods of this kind were not considered for appreciable liquid production of more than 5 mol % of the nitrogen product quantity.
The invention is based on the object of indicating a method of the type mentioned in the introduction and a corresponding apparatus, which are suitable for relatively high liquid production of 6 to 10 mol % of the nitrogen product quantity or more, with a relatively high nitrogen product yield in the method of approximately 60%, and which moreover are efficient to run. (The nitrogen yield is dependent on other parameters, for example the product purity.)
This object is achieved with all of the features as described herein
In this context, a second compressed nitrogen stream is drawn off from the top of the high-pressure column and is expanded, in a second expansion machine, to a pressure which still allows this stream to be drawn off as a compressed product, preferably to approximately the pressure of the first compressed nitrogen stream from the top of the low-pressure column. Also, part of the nitrogen condensed in the low-pressure-column top condenser is drawn off as a liquid nitrogen product.
This makes it possible to generate, with minimal additional effort, the cold which is required for the greater liquid production. The second turbine, with a different inlet temperature compared to the first turbine, also improves the temperature profile in the main heat exchanger (lower thermodynamic losses as a consequence of smaller temperature differences).
In the invention, preferably more than 90 mol % of the gaseous nitrogen product is obtained at the same pressure, namely that of the low-pressure column.
Applications are known which require relatively large quantities of liquid product (LIN) in addition to large quantities of compressed nitrogen at approximately 8 bar. These applications include, for example, petrochemical complexes or gas stations with on-site gas supply to clients in the semiconductor industry. In that context, the liquid product is used either to cover spikes in demand (these can be considerable, especially in the case of petrochemical plants) and/or to serve the external liquid market. (The above pressure indication—and all subsequent ones, unless otherwise stated—is to be understood as absolute pressure.)
Hitherto, these objects were achieved for example by using “Spectra” methods (see e.g. U.S. Pat. No. 4,966,002 or 5,582,034) in combination with an external, intermittently-operated condenser. Alternatively, only Spectra plants are used, wherein liquid production is temporarily accomplished at the cost of greatly reduced gas supply. The first case practically requires two plants, which implies particularly high investment costs. In the second case, although only one plant is used, this has very limited capacity for liquid production; especially in the case of 8 bar embodiments, liquid production is not only limited but also inefficient owing to a relatively small pressure gradient in the turbine; it is generally not capable of providing the desired supply of liquid. Furthermore, the efficiency of the Spectra process is relatively low compared to the two-column method used in the invention.
The method according to the invention is particularly expedient to carry out if the first compressed nitrogen stream is drawn off from the top of the low-pressure column at a pressure of 8.0 to 9.0 bar, in particular 8.4 to 9.0 bar.
Preferably, the second compressed nitrogen stream is expanded in the expansion machine to approximately the pressure of the first compressed nitrogen stream; the two compressed nitrogen streams are then united and are drawn off as a common compressed nitrogen product stream. The simplest option is for this unification to take place within the main heat exchanger, although it can in principle also take place in the warmth, that is to say downstream of the main heat exchanger.
The two inlet temperatures of the expansion machines are preferably different in particular the second intermediate temperature is at least 10 K higher than the first intermediate temperature. For example, the temperature difference is between 90 and 30 K, preferably between 70 and 50 K.
In a first variant of the invention, both expansion machines are coupled to a generator or to a dissipative brake. Use is preferably made of generator turbines. Although this does not directly return any energy back to the process, this variant is particularly flexible with respect to different load cases.
Less flexible but more cost-effective is a second variant of the method according to the invention, in which the two expansion machines each drive one compressor stage, and a process stream is compressed sequentially in the two compressor stages. Alternatively, it is possible for just one of the two turbines (for example the compressed nitrogen turbine or “second expansion machine”) to be coupled to a compressor stage, and for the other (for example the residual gas turbine or “first expansion machine”) to be coupled to a generator.
This process stream can for example consist of one of the following streams:
Preferably, however, the low-pressure-column top condenser is designed, on its evaporating side, as a forced-flow evaporator. This produces no loss of hydrostatic pressure on the evaporating side and also a comparatively low pressure on the condensing side.
Alternatively or additionally, the main condenser is designed, on its evaporating side, as a forced-flow evaporator. This produces, in comparison to a bath evaporator, a lower loss of hydrostatic pressure on the evaporating side and also a comparatively low pressure on the condensing side.
In another embodiment of the invention, in the first operating mode, at least one part of the condensed nitrogen is evaporated under pressure and is then obtained as a compressed nitrogen product. The corresponding evaporation device is operated using external heat, that is to say that the heat source is in particular not a process stream of the cryogenic separation system. In the second operating mode, no condensed nitrogen, or only a smaller quantity than in the first operating mode (for example less than 50%), is evaporated in the evaporation device. The evaporation device has, in particular, an air-heated evaporator, a water bath evaporator and/or a solid material cold store.
The invention also relates to a device for producing compressed nitrogen and liquid nitrogen by cryogenic separation of air. The apparatus according to the invention can be complemented by apparatus features which are further described herein.
By way of example, the method according to the invention uses the following pressures and temperatures:
Operating pressures (in each ease at the top of the columns):
Low-pressure-column top condenser:
Air pressures:
The invention—and further details of the invention—are explained in more detail below with reference to exemplary embodiments represented schematically in the drawings, in which:
In
Line 7 conveys all of the purified feed air (with the exception of relatively small branch-offs, for example for instrument air) to the main heat exchanger 8, where it is cooled on its path to the cold end. The cold, completely or almost completely gaseous air 8 is introduced into the high-pressure column 9. The high-pressure column 9 is part of a distillation column system also containing a low-pressure column 10, a main condenser 11 and a low-pressure-column top condenser 12. Both of the condenser-evaporators 11, 12 are designed, on their evaporating side, as forced-flow evaporators.
Liquid crude oxygen 13 from the sump of the high-pressure column 9 is cooled in a counter-current subcooler 14, and is fed via line 15 to an intermediate point of the low-pressure column 10. A first part 17 of the gaseous top nitrogen 16 of the high-pressure column 9 is drawn off as a second compressed nitrogen stream and is supplied to the main heat exchanger 8. A second part 20 of the gaseous top nitrogen 16 is at least partially condensed in the condensing space of the main condenser 11. A first part of the resulting liquid nitrogen 21 is used as a recirculation flow in the high-pressure column 9. The remainder 22/23 is cooled in the counter-current subcooler 14 and is fed to the top of the low-pressure column 10.
A liquid, oxygen-rich fraction 24 from the sump of the low-pressure column, or from the condensing space of the main condenser 11, is cooled in the counter-current subcooler 14 and is fed, as a coolant stream, via line 25 to the evaporating space of the low-pressure-column top condenser 12 where it is at least partially evaporated. The vapour produced in the evaporating space of the low-pressure-column top condenser 12 is drawn off as a residual gas stream 26 and is heated in the main heat exchanger 8 to a first intermediate temperature of for example 142 K. The residual gas stream 27, at the first intermediate temperature, is fed into a first expansion machine 28, in this case in the form of a generator turbine, where it is expanded, in a work-performing manner, to just above atmospheric pressure. The residual gas stream 29 expanded in a work-performing manner is fully heated in the main heat exchanger 8, that is to say is heated to roughly ambient temperature.
The warm residual gas 30 can be discharged directly to the atmosphere (ATM) via line 31. Alternatively or partially, it can be used, via line 32, as regeneration gas in the purification device 6, possibly after heating in a regeneration gas heater 33. Used regeneration gas is discharged to the atmosphere via line 34.
A first part 44 of the gaseous top nitrogen from the low-pressure column 10 is drawn off as a first nitrogen stream, is heated in the main heat exchanger 8 and is drawn off 18, 19 as a first compressed nitrogen product (PLAN). A second part 45 of the gaseous stop nitrogen of the low-pressure column 10 is at least partially condensed in the condensing space of the low-pressure-column top condenser 12. A part 47 of the nitrogen 46 condensed in the low-pressure-column top condenser 12 is drawn off as a liquid nitrogen product (PUN).
The second compressed: nitrogen stream 17 from the high pressure column 9 is—heated in the main heat exchanger 8 to a second intermediate temperature of 207 K. The second compressed nitrogen stream 40, at the second intermediate temperature, is fed into a second expansion machine 41 where it is expanded, in a work-performing manner, to approximately the operating pressure at the top of the low-pressure column 10. Here, the second expansion machine 41 is also designed as a generator turbine. The second compressed nitrogen stream 42, expanded in a work-performing manner, is fully heated in the main heat exchanger. The warm second compressed nitrogen stream 43 is united with the warm first compressed nitrogen stream 18 and is drawn off via line 19, together with the first compressed nitrogen product, as a second compressed nitrogen product (PLAN).
The methods of both of
Optionally, one part 50 of the second compressed nitrogen stream 17 from the high-pressure column 9 can be fed as far as the warm end of the main heat exchanger 8 and can be discharged as a high-pressure product HPGAN at a pressure of 13 to 14 bar (not shown).
In
By contrast, in
In the case of relatively low pressures (for example below 3 bar) in the evaporating space of the low-pressure-column top condenser 12, it is expedient to undertake additional measures, for example the enrichment of propane at an acceptable point in the plant, and the disposal of this enriched liquid from the rectifier system (for example to the ejector, into the surroundings or into the impure nitrogen stream prior to release to the atmosphere). The enrichment can then take place in a known manner directly in the high-pressure column by using the barrier plates.
Because of the relatively high liquid production, the air is already pre-condensed at the inlet into the high-pressure column (for example to a degree of approximately 1% or more). The liquid present owing to this pre-condensation is then separated in the sump and can be discarded together with the flushing liquid. However, this substantially reduces the efficiency of the method since it wastes a lot of cold and also a lot of nitrogen molecules.
A solution to this problem can be found in the method of
The high-pressure column has one to five practical plates as bather plates 663. The liquid crude oxygen 13 is drawn off above the barrier plates and the high-pressure-column flushing liquid 661 is drawn off below, namely directly from the sump; it contains both the recirculation liquid from the high-pressure column or from the barrier plates, and also the pre-condensed air introduced via line 8. The stream 661 is fed to the top of the auxiliary column 660 (possibly after subcooling), is enriched in low-volatility components during the exchange of material within the column, and is finally drawn off—in substantially smaller quantity—from the sump of the auxiliary column 660 via line 662. The quantity drawn off is for example approximately 40 to 50 Nm3/h; in relative terms, for a total air quantity of 100,000 Nm3/h the ratio of stream quantities 662 to 661 is for example between 1% and 10%. The sump evaporator 664 of the auxiliary column 660 is heated using gaseous air 665 from the high-pressure column 9. The air 666 condensed in the sump evaporator 664 is fed to the low-pressure column 10. The top gas 667 produced in the auxiliary column 660 is also fed to a suitable point of the low-pressure column 10.
The C3H8 from the air part stream 665 to the condenser of the auxiliary column 660 is retained in the system. However, this quantity of air is relatively small (approximately 1%) compared to the quantity of feed air, and so operational reliability is not influenced thereby. By virtue of the fact that the flushing 662 is now taken from the auxiliary column 660, it is possible to increase the recirculation quantity to the barrier section 663 in the high-pressure column. Thus, more xenon is flushed out and the actual flushing quantity 662 from the auxiliary column can also be used and processed further as a xenon concentrate; in a method according to
Deviating from the depiction in
The method described hitherto has only limited flexibility in operating situations with relatively low liquid production (that is to say deviating from the design situation). Such cases cause a drop in the pressure in the evaporating space of the upper condenser—and thus also in the inlet pressure into the residual gas turbine and the intake pressure in the case of a possible downstream post-compressor; this relates in particular to the use for blending natural gas in order to adjust the calorific value. However, a significantly reduced intake pressure for the post-compressor has a significant effect on the dimensioning of the machine and also imposes a limit on the normal underload behaviour.
A comparatively cost-effective and yet relatively efficient solution to the situation is possible with the system shown in
In the discharge phase, either the power of the main air compressor or the power of the nitrogen product compressor(s) is reduced, or alternatively these remain unchanged and more gaseous product is obtained. It is of course possible for two or three of these measures to be used in combination.
Especially in the case of relatively high product output pressures or intermediate pressures it can be expedient to employ this solution since the saving in terms of compressor power at the product compressor is ever greater with increasing pressure.
In a second operating mode, less or no liquid product is evaporated. For example, those additional method steps which are used in the first operating mode are abandoned.
In contrast to
At least part of the liquid nitrogen 47 is stored in a liquid nitrogen tank 870. Preferably, this liquid nitrogen tank 870 also serves for the output of liquid product (not shown in
In a second operating mode, the atmospheric evaporator 873 is shut off and the entire liquid production PLIN is output as end product or is stored in the liquid nitrogen tank 870.
Number | Date | Country | Kind |
---|---|---|---|
16001534 | Jul 2016 | EP | regional |
Number | Name | Date | Kind |
---|---|---|---|
3375673 | Cimler | Apr 1968 | A |
4453957 | Pahade | Jun 1984 | A |
4617036 | Suchdeo | Oct 1986 | A |
5901576 | Agrawal et al. | May 1999 | A |
6694775 | Higginbotham | Feb 2004 | B1 |
20050126221 | Ha et al. | Jun 2005 | A1 |
20100242537 | Lochner | Sep 2010 | A1 |
20110083469 | Alekseev | Apr 2011 | A1 |
20140007617 | Le Bot | Jan 2014 | A1 |
20160187060 | Kirchner | Jun 2016 | A1 |
20170299261 | Narinsky | Oct 2017 | A1 |
Number | Date | Country |
---|---|---|
4441920 | Apr 1996 | DE |
1022530 | Jul 2000 | EP |
Number | Date | Country | |
---|---|---|---|
20180017322 A1 | Jan 2018 | US |