Patent Grant
11435139
This application is a § 371 of International PCT Application PCT/FR2018/052776, filed Nov. 8, 2018, which claims the benefit of FR1761346, filed Nov. 29, 2017, both of which are herein incorporated by reference in their entireties.
The present invention relates to a method and to an apparatus for separating air by cryogenic distillation.
In an apparatus for separating air using low-pressure single-column distillation to separate the air, it is sought to produce argon without having rich liquid from a medium-pressure column to operate the condenser of the argon column.
The invention consists in using a portion of a nitrogen cycle which provides the reboiling and the reflux for the single column operating at low pressure to operate the condenser of the argon column.
Without overcomplicating the scheme of the method, this additionally makes it possible to benefit from a high degree of operational flexibility: in the event of a rush of nitrogen into the argon column, it is possible to ensure condensation continues at the top of the argon column, and therefore to maintain oxygen production without the risk of the argon column, and then the low-pressure column, stopping.
In addition, the proposed scheme is better in energy terms than those of the prior art, in particular for high argon yields.
A person skilled in the art could design a single-column apparatus operating at low pressure (or LP) with a nitrogen cycle and with draw-off of a rich pseudo-liquid at an intermediate point of the LP column to feed the condenser of the argon column. This liquid could be taken between the top of the column and the draw-off of gas enriched in argon sent to the argon column. The liquid would be pumped to arrive at the condenser of the argon column, where it would be vaporized and would then be sent to the LP column at a level below the liquid draw-off point.
According to one subject of the invention, what is provided is a method for separating air by cryogenic distillation in a column system comprising a first column operating at a first pressure and a second column operating at a second pressure, the first pressure being substantially equal to the second pressure, wherein:
i) compressed, purified and cooled air is sent to an intermediate point of the first column, a liquid enriched in oxygen is drawn off from the bottom of the first column and/or a gas enriched in oxygen is drawn off from the first column and a flow enriched in nitrogen is drawn off from the top of the first column;
ii) a flow enriched in argon is sent from an intermediate point of the first column to the bottom of the second column and a flow rich in argon is drawn off from the top of the second column;
iii) the flow enriched in nitrogen is compressed in a compressor and the compressed flow is used to heat a bottom reboiler of the first column, producing an at least partially condensed flow enriched in nitrogen;
iv) the at least partially condensed flow enriched in nitrogen is divided into first and second portions, the first portion is sent to the top of the first column after an expansion step and the second portion is sent to a top condenser of the second column after an expansion step in which the second portion is at least partially vaporized to form an auxiliary flow, characterized in that
According to other optional aspects:
According to another aspect of the invention, what is provided is an apparatus for separating air by cryogenic distillation in a column system comprising a first column operating at a first pressure and having a bottom reboiler and a second column operating at a second pressure having a top condenser, the first pressure being substantially equal to the second pressure, a compressor, a turbine, a pipe for sending compressed, purified and cooled air to an intermediate point of the first column, a pipe for drawing off a liquid enriched in oxygen from the bottom of the first column and/or a gas enriched in oxygen from the first column and a pipe for drawing off a flow enriched in nitrogen from the top of the first column and for sending it to the compressor, a pipe for sending a flow enriched in argon from an intermediate point of the first column to the bottom of the second column, a pipe for drawing off a flow rich in argon from the top of the second column, a pipe for sending the flow enriched in nitrogen compressed in the compressor to the bottom reboiler of the first column in order to produce an at least partially condensed flow enriched in nitrogen, means for dividing the at least partially condensed flow enriched in nitrogen into first and second portions, means for sending the first portion to the top of the first column after an expansion step, means for sending the second portion to the top condenser of the second column after an expansion step in which the second portion is at least partially vaporized to form an auxiliary flow, means for sending the auxiliary flow to the turbine where it is at least partially liquefied and means for sending the at least partially liquefied flow to the top of the first column, these means potentially comprising a phase separator for separating the liquid and gas formed in order for them then to be sent separately to the first column.
According to other optional aspects of the invention:
In certain embodiments, the invention consists in using a portion of the nitrogen cycle which provides the reboiling and the reflux for the LP single column to operate the condenser of the argon column.
The cycle nitrogen can be condensed in the vaporizer of the LP column. A portion of the nitrogen can be completely, preferably partially, subcooled and sent into the condenser of the argon column.
In the condenser, it is vaporized at an intermediate pressure between the pressure of the nitrogen cycle and the pressure of the LP column, the vaporization thereof making it possible to condense the upflowing vapor in the argon column to provide the reflux for the argon column.
The nitrogen vaporized at an intermediate pressure is then expanded in a turbine toward the top of the LP column. Since this turbine is very cold, what is obtained at the outlet is a partially two-phase mixture, the liquid portion also contributing to the reflux for the LP column. The cold produced by the turbine allows all or some of the cooling power to be applied to outputting the argon produced directly in liquid form, to be sent to storage for example.
In the event of a rush of nitrogen into the argon column, it will be possible to continue to provide a reflux in the argon column by decreasing the intermediate pressure so as to lower the temperature of the vaporized nitrogen, which makes it possible to continue condensing the upflowing vapor which is loaded with nitrogen and hence has become colder. Argon draw-off is stopped because it does not meet the nitrogen specification. The cooling power of the turbine is significantly decreased because the intermediate pressure has been decreased, but that does not matter because liquid argon is no longer being produced.
Keeping the argon column in operation avoids disrupting, or even stopping the LP column (through the liquid held in the argon column being sent in quantity to the LP column), which allows the reliability of oxygen production to be increased, regardless of disruptions for the argon column.
The nitrogen rush may be evacuated for example by purging at the condenser of the argon column or the top of the argon column, while keeping the argon column operating with respect to the difficult argon/oxygen separation.
Once the nitrogen rush has been evacuated, there is an immediate return to argon production with good nitrogen and oxygen specifications, unlike a more conventional apparatus in which a nitrogen rush will stop the argon column, requiring the stock of liquid in the argon column to be entirely renewed when it is restarted.
This high tolerance makes it possible to have an operation when running that gets very close to the maximum achievable argon yield for the process operation in question, without taking an operational margin to avoid unwanted stoppages due in particular to nitrogen rushes.
Similarly, it makes it possible, by minimizing operational risks, to facilitate the omission of the denitrogenation column for purifying the argon produced by the argon column of nitrogen, by adding a few theoretical plates directly above the argon tap in the LP column, in order to substantially decrease the nitrogen content before entering the argon column.
It is needless, in operation, to purge the bath of the condenser of the argon column, since there is no liquid rich in oxygen and potentially in air secondary impurities. Purging may be of use only when stopped, for example to empty the bath of cryogenic liquid.
Further features, advantages and possible applications of the invention are apparent from the following description of working and numerical examples and from the drawings. All described and/or depicted features on their own or in any desired combination form the subject matter of the invention, irrespective of the way in which they are combined in the claims the way in which said claims refer back to one another.
The invention will be described in greater detail with reference to the figures.
The column 1 operates between 1.013 bara and 2 bara, for example at 1.3 bara.
The argon column 2 operates at between 1.013 bara and 2 bara, for example at 1.3 bara.
In this example, both columns operate at the same pressure.
Air that has been compressed and purified of water and of carbon dioxide 3 is cooled in a heat exchanger 5 and sent to an intermediate point of a separation column 1. The air is separated by distillation to produce liquid enriched in oxygen at the bottom of the column and nitrogen gas 7 at the top of the column. At an intermediate level of the column and below the air inlet, a flow 47 enriched in argon is withdrawn and sent to an argon column 2. Liquid argon or argon gas 51 is produced at the top of the column 2 and the bottom liquid 49 is sent to the column 1 at the draw-off level of the column 1. Neither the liquid 49 nor the gas 47 are pressurized or expanded between the two columns (beyond pressure drops and hydrostatic heads).
The apparatus is kept cold and carries out distillation by virtue of a nitrogen cycle. The nitrogen taken from the top of the column 1 is used to cool a heat exchanger 11 and is then divided into two, one portion 9 being heated in the heat exchanger 5 and one portion 13 being used to produce cold and to supply the energy for distillation. The nitrogen 13 is heated in a heat exchanger 15, compressed in a compressor 19, cooled in the cooler 21 to form the flow 23 and then returned to the exchanger 15. In the exchanger 15, the flow 23 is divided into two. A portion 29 is cooled as far as the cold end of the exchanger 15 and is then used to heat the bottom reboiler 31 of the column 1. The rest of the nitrogen 25 at an intermediate temperature from the exchanger 15 is expanded in a turbine 27 and rejoins the nitrogen 13 to return to the exchanger 15.
After having been used to heat the reboiler 31, the nitrogen 29 which has been condensed is cooled in the subcooler 11 and then divided into two. The nitrogen 29 may be divided into two before the subcooler, allowing the two portions to be subcooled differently.
One portion 33 is expanded in a valve and then sent as a reflux liquid to the top of the column 1. The other portion 35 is sent, at a pressure higher than that of column 1, to the top condenser 37 of the column 2 where it is at least partially vaporized. The nitrogen 39 thus formed is expanded in the turbine 41 and the expanded flow 43 feeds the top of the column 1, to potentially passing through a separating vessel and sending the liquid, itself potentially pumped, and the gas through two separate pipes.
The portion 35 of the nitrogen from the subcooler, which is sent to the condenser 37 of the argon column 2, is very cold, which creates a risk of crystallization. To prevent this problem, it is possible:
The nitrogen 43 expanded in the turbine 41 is partially liquefied at the outlet of the turbine wheel, or even in the wheel, the prevailing pressure and temperature conditions at the outlet of the wheel being such that, for example, half of the isentropic expansion has taken place. The liquid content in the wheel or at the outlet of same is then between 0.5% and 10%, preferably between 2% and 5%.
If it is desired to limit the liquid content to prevent mechanical damage to the turbine, it is possible to envisage heating the nitrogen 39 before expansion, for example in the subcooler 11. The rest of the expansion takes place in the volute of the turbine where at least some of the rest of the gas continues to be cooled and liquefied. The liquid portion thus formed thus contributes to the reflux for the LP column 1.
There is also the possibility of providing a pipe for liquid argon to the liquid nitrogen which goes to the top of the column 1, in the case of argon production being lower than the production at optimum argon yield, to benefit from an additional liquid reflux at the top of the LP column and therefore gain in energy efficiency. This pipe may go directly to the top of the LP column or be connected to a separating vessel at the outlet of the turbine.
The architecture of the apparatus may be a conventional architecture, namely one using one-piece columns of circular cross section, fitted with structured packings or plates.
However, it is also possible to use the novel architecture from FR3052242, FR3052243, FR3052244 or FR3059087. According to this architecture, the column is replaced with a stack of modules of square or rectangular cross section, each module being insulated and containing an element allowing material and heat exchange, such as packings. Separation takes place at low temperature by distillation, the liquids being distilled downflowing from one module to another and the gases upflowing from one module to another. In this way, the fluid to be separated is introduced into one module and a fluid enriched in a component of the fluid exits from another module of the same stack.
An argon option may be defined which consists of inserting a module at an intermediate position of the LP column, at the level of the argon bulge and the cold box, without having to modify the rest of the equipment. The possible lengthening of the LP column is used to advantage to add theoretical plates above the draw-off of the argon mixture in order to substantially decrease the nitrogen content at the argon bulge and therefore to omit the denitrogenation column, which simplifies the implementation of the argon option.
In the basic version, the liquid nitrogen condensed in the vaporizer, then subcooled, is expanded in a valve and then sent through a pipe in two-phase form to the top of the LP column.
In the version with argon option, it is partially expanded in the same valve and sent through the same pipe to the inserted module where one portion is partially expanded, and then sent to the condenser of the argon column, and the other portion is completely expanded and sent to the top of the LP column through the same pipe as in the basic version.
The partially expanded portion is vaporized, and then turbined:
The inserted module also comprises piping/duct extensions for connecting the piping/duct extensions which are placed along the LP column at the level of the argon bulge.
In this configuration of the invention, the nitrogen cycle remains unchanged between the option without argon and the option with argon, with oversizing of the equipment (in particular nitrogen cycle compressor) being limited to 10%, or even 5%, or even without any oversizing. It is therefore easy to standardize and/or to modularize it to satisfy both options.
The ad hoc addition of the turbine to the argon condenser makes it possible to provide the necessary cooling power to liquefy argon, without affecting the rest of the cold balance of the apparatus.
In energy terms, the invention rates particularly well in comparison with the prior art, in particular at high argon yield as illustrated in
The gain is increased by the lack of need to take margins with respect to the operation of the separation apparatus.
Potentially, an external nitrogen cycle is used to partly heat the bottom reboiler of the low-pressure column, the rest of the heating being provided by the gas from the top of the MP column.
Those of ordinary skill in the art will recognize that identical pressures are difficult, if not impossible, to maintain during operation. As such, substantially equal in pressure is meant to encompass pressures that would be recognized in the industry as being the same but for naturally occurring variances and/or internal pressure drops. In certain embodiments, there can be an absence of pressure modifying means disposed between the two columns, such that the pressure of fluids flowing between the two columns is not intentionally increased or decreased by compressors, expansion valves, turbines, or the like.
While the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the appended claims. The present invention may suitably comprise, consist or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed. Furthermore, if there is language referring to order, such as first and second, it should be understood in an exemplary sense and not in a limiting sense. For example, it can be recognized by those skilled in the art that certain steps can be combined into a single step.
The singular forms “a”, “an” and “the” include plural referents, unless the context clearly dictates otherwise.
“Comprising” in a claim is an open transitional term which means the subsequently identified claim elements are a nonexclusive listing (i.e., anything else may be additionally included and remain within the scope of “comprising”). “Comprising” as used herein may be replaced by the more limited transitional terms “consisting essentially of” and “consisting of” unless otherwise indicated herein.
“Providing” in a claim is defined to mean furnishing, supplying, making available, or preparing something. The step may be performed by any actor in the absence of express language in the claim to the contrary.
Optional or optionally means that the subsequently described event or circumstances may or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not occur.
Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within said range.
All references identified herein are each hereby incorporated by reference into this application in their entireties, as well as for the specific information for which each is cited.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1761346 | Nov 2017 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/FR2018/052776 | 11/8/2018 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2019/106250 | 6/6/2019 | WO | A |
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| 2934907 | Scofield | May 1960 | A |
| 4057407 | Bigi | Nov 1977 | A |
| 4756731 | Erickson | Jul 1988 | A |
| 4783208 | Rathbone | Nov 1988 | A |
| 4818262 | Brugerolle | Apr 1989 | A |
| 4883516 | Layland | Nov 1989 | A |
| 20010052243 | Davidian | Dec 2001 | A1 |
| 20080029381 | Dubettier | Feb 2008 | A1 |
| Number | Date | Country |
|---|---|---|
| 2 705 141 | Nov 1994 | FR |
| 3 052 242 | Dec 2017 | FR |
| 3 052 243 | Dec 2017 | FR |
| 3 052 244 | Dec 2017 | FR |
| 3 059 087 | May 2018 | FR |
| 1 258 568 | Dec 1971 | GB |
| Entry |
|---|
| International Search Report and Written Report for PCT/FR2018/052776, dated May 16, 2019. |
| Agrawal, R., et al., “Heat Pumps for Thermally Linked Distillation Columns: An Exercise for Argon Production from Air,” Industrial & Engineering Chemistry Research, vol. 33, No. 11, Jan. 1, 1994, pp. 2717-2730. |
| Number | Date | Country | |
|---|---|---|---|
| 20200370825 A1 | Nov 2020 | US |
