• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    In an air separation process by cryogenic distillation, air (1,7) is compressed at a first pressure, purified, cooled in a heat exchanger (17) and sent for separation in a column system ( 31,33), at least a portion (9) of the purified air exits at an intermediate level of the heat exchanger, is supercharged in at least one booster (13,15), having a variable compression ratio at a intermediate temperature of the heat exchanger, is returned to the heat exchanger for cooling and is sent to the column system and if the compression ratio of the booster or at least one of the boosters or boosters is above At a threshold, the gaseous oxygen flow rate (55) of the column system is not withdrawn and if the compression ratio of the booster or at least one of the boosters or boosters is below the threshold, a flow rate of gaseous oxygen is drawn off from the column system and is re heats up in the heat exchanger.
    公开号:FR3014545A1
    申请号:FR1362152
    申请日:2013-12-05
    公开日:2015-06-12
    发明作者:Bertrand Demolliens
    申请人:Air Liquide SA；LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a method and apparatus for air separation by cryogenic distillation.
    [0002] In particular, it relates to an air separation process in which a liquid produced by the distillation of air vaporizes in a heat exchanger by heat exchange with air, at least a portion of which has been compressed in a compressor having an inlet temperature lower than the ambient temperature, called "cold booster".
    [0003] The exchange diagram of an air separation apparatus using a cold booster process, illustrated in Figure 1, is mainly characterized by the presence of two offset air liquefaction (L) and vaporization stages. oxygen (V). All that is needed is a single main air compression machine called MAC HP ("main air compressor -high pressure" or "main-high-pressure air compressor") delivering 15-25 bars. Generally, an ASU consists of a MAC driving at about 6 bar and a BAC air blower aspirating at 6 bars and compressing this air at a pressure such that the liquefaction temperature of the air HP is equal to the Oxygen vaporization temperature near approach. (Case bearings face to face) We differentiate the booster according to the MAC, the BAC, a compressor driven by energy external to the process (example: engine, steam turbine, gas turbine ... etc) of a booster said in English "booster" driven by energy recovered in the process (expansion of a gas).
    [0004] According to an object of the invention, there is provided a method of air separation by cryogenic distillation in which: i) air is compressed at a first pressure, purified, cooled in a heat exchanger and sent to be separated in a column system ii) at least a portion of the purified air exits at an intermediate level of the heat exchanger, is supercharged in at least one booster, optionally in two series boosters, having a variable compression ratio to an intermediate temperature of the heat exchanger, is returned to the heat exchanger to cool and is sent to the column system iii) a liquid flow is withdrawn from the column system, pressurized and vaporized in the heat exchanger for forming a gaseous product enriched in a component of the air and a) if the compression ratio of the booster or at least one of the boosters or boosters is above a threshold, it does not withdraw no gaseous oxygen flow rate of the column system and if the compression ratio of the booster or at least one of the boosters or boosters is below the threshold, a flow of gaseous oxygen is withdrawn from the column system and heats up in the heat exchanger or b) if the compression ratio of the booster or at least one of the boosters or boosters is above a threshold, a first rate of gaseous oxygen equal to at most 2 is withdrawn % of the gaseous product (81) rich in oxygen and is heated in the heat exchanger and if the compression ratio of the booster or at least one of the booster or booster is below the threshold, a gaseous oxygen flow rate greater than the first flow rate is withdrawn from the column system and heats up in the heat exchanger. According to other optional objects: - if the compression ratio of the booster or at least one of the boosters or boosters is above a threshold, no liquid is produced as the final product or a first quantity of product is produced. liquid as final product and if the compression ratio of the booster or at least one of the boosters or boosters is below the threshold, liquid is produced as the final product or a quantity of liquid is produced as final product greater than the first quantity. a nitrogen-enriched flow is withdrawn from the column system, the oxygen gas flow rate is mixed with the nitrogen-enriched flow rate to form a mixed flow rate and the mixed flow rate is heated in the heat exchanger. the flow rate of oxygen gas or the mixed flow rate is sent to the air. - Only a portion of the purified air is supercharged in the booster or boosters and another part of the air is cooled in the heat exchanger and expanded in a turbine coupled to the booster or in turbines coupled to the boosters. - The compression ratio of the booster or at least one of the boosters is detected by measuring the air flow expanded in the turbine or turbines. the air pressure upstream and downstream of the booster or at least one of the compressors is measured to detect the compression ratio thereof or of these. a gaseous product rich in oxygen is produced by withdrawing an oxygen-rich liquid from the column system and vaporizing it in the heat exchanger. - The oxygen gas flow, withdrawn in case of compression ratio of the booster too low, is at most 10% of the gaseous product rich in oxygen. if the compression ratio of the booster or of at least one of the booster or booster is above a threshold, a first flow of gaseous product rich in oxygen is produced by withdrawing an oxygen-rich liquid from the column system and by vaporizing it in the heat exchanger and if the compression ratio of the booster or at least one of the boosters or boosters is below the threshold, a reduced oxygen-rich gas product flow is produced compared to the first flow rate According to another object of the invention, there is provided an apparatus for separating air by cryogenic distillation comprising a heat exchanger, a column system, at least one booster having a variable compression ratio, a pipe for sending air compressed air at a first pressure, purified and cooled from the heat exchanger to the column system to be separated, means for outputting at least a portion of the purified air at a level of intermediate heat exchanger and to send it to the booster or booster in series at an intermediate temperature of the heat exchanger, means for returning the supercharged air in the booster or booster to the heat exchanger for cooling down and being fed to the column system, a pipe for withdrawing a liquid flow from the column system, means for pressurizing the liquid flow and a pipe for sending the pressurized liquid flow to vaporize in the heat exchanger to form a gaseous product enriched in a component of the air, characterized in that it comprises means for detecting the compression ratio of the booster or at least one of the booster pumps, means for withdrawing a flow rate of gaseous oxygen from the booster system. columns and means for varying the rate of gaseous oxygen withdrawn from the column system as a function of the compression ratio (s) of the booster or at least one of the booster urpresseurs. According to other optional aspects: the apparatus comprises at least two serially connected boosters; the apparatus comprises means for short-circuiting at least one of the at least two boosters; the apparatus comprises means for voluntarily stopping one of the boosters; two boosters which can be short-circuited - the column system comprises a first column operating at a first pressure and a second column operating at a second pressure, the second pressure being less than the first pressure, the two columns being thermally connected between they by means of a vaporizer-condenser - the means for withdrawing the flow of oxygen gas are connected to the tank of the second column and / or the vaporizer-condenser 15 - the means allowing the flow of oxygen gas are constituted by a valve - the apparatus comprises means for withdrawing a nitrogen enriched flow from the column system, means for mixing the flow of oxygen With the nitrogen enriched flow to form a mixed flow and means for sending the mixed flow, the gas is heated to the heat exchanger. the apparatus comprises means for sending the flow of oxygen gas or the mixed flow rate to the air. the apparatus comprises means for sending only a portion of the purified air to be supercharged in the booster or the boosters and means for sending another part of the air to cool in the heat exchanger and to relax in a turbine coupled to the booster or in the turbines coupled to the boosters. the apparatus comprises means for detecting the compression ratio of the booster or at least one booster by measuring the expanded air flow rate in the turbine or turbines. the apparatus comprises means for measuring the pressure of the air upstream and downstream of the booster or the boosters to detect the compression ratio thereof or the booster - the apparatus comprises means for withdrawing a liquid The oxygen-rich column system and means for sending it to vaporize in the heat exchanger to produce a gaseous product rich in oxygen. The invention will be described in more detail with reference to the figures which show methods according to the invention. the invention. Figure 1 illustrates a typical arrangement of turbines and boosters in a cold booster process. Here the air 1 is compressed in a compressor 3 to a pressure between 12 and 30 bar abs and cooled to around room temperature by means of an air-water exchanger (with direct or indirect contact). It will then be cleaned in the head to remove some impurities such as water and CO2. This current will then be divided into two parts. Part 9 is supercharged in a booster booster 13, cooled to around ambient temperature by means of an air-water exchanger (with direct or indirect contact), then cooled in a heat exchanger 17 to an intermediate temperature of it, compressed in a cold booster ("booster") and again cooled in the heat exchanger 17, and liquefied against the product stream before being sent to the distillation. The other part 11 of the air 7 is then cooled to an intermediate temperature of the exchanger 17, possibly colder than the inlet temperature of the booster 15. At this temperature, the part 11 is divided in two. Each portion 23,25 is sent to a respective turbine 21,19 and the expanded flow rates are mixed to form a flow rate to be distilled 27. The flow 27 is sent in gaseous form to the distillation. The energy recovered by the detents of the turbines 19 and 21 serves to drive the booster booster 13 and 15.
    [0005] If the compression ratio of the cold booster reduces, there is an increase in the gap at the cold end of the exchange diagram because it consumes less heat. However, in this case, the liquefaction stage shifts, taking place at a lower temperature and will tend to cross the exchange diagram, in which case no heat exchange is possible.
    [0006] It is therefore an object of the present invention to allow a reduction in the compression ratio of the cold booster, reducing the risk of malfunction.
    [0007] In the event of a reduction in the compression ratio, gaseous oxygen is withdrawn at the low pressure column, which may be rejected in the residual nitrogen. The invention will be described in more detail with respect to Figure 2 which shows a method according to the invention. In Figure 2, we see a heat exchange part on the left where the illustrated arrangement could be replaced by that of Figure 1. To the right, the column system here is a double column, comprising a first column 31 operating to a first pressure and a second column 33 operating at a second pressure lower than the first pressure, the two columns being thermally connected to each other at least one vaporizer-reboiler 35. The figure represents the case where the columns are side by side but nothing prevents them from being superimposed. Here the air 1 is compressed in a compressor 3 to a pressure between 15 and 15 bar abs and purified in the unit 5 (not shown in Figure 2) before being divided into two. A portion 9 is supercharged in a booster 13, cooled in the exchanger 17 to an intermediate temperature thereof, supercharged again in the cold booster 15 and then sent to the exchanger 17 to be cooled. The cooled air coming from the cold booster 15 leaves the exchanger 17, is divided in two, a part 61 being sent to the first column 31 after expansion in one valve and the other part 63 being sent to the second column 33 after relaxation in another valve. Thus the two boosters 13,15 are connected in series while in Figure 2 they are in parallel.
    [0008] The remainder 11 of the air 1 is cooled in the exchanger to a temperature below the inlet temperature of the cold booster 15. At this temperature, the air 11 is divided in two. The portion 23 is expanded in a first turbine 21. The portion 25 is expanded in a second turbine 19. The two expanded flow rates are combined to form the gas flow 27 and the air is sent to the bottom of the first column 31 operating at a temperature of 30.degree. pressure between 3 bar and 14 bar (but typically around 5.5-6 bar). The air separates in the first column 31 to form an oxygen-enriched liquid 37 which is sent from the first column 31 to the second column 33. A nitrogen-rich liquid is sent from the top of the first column 31 to the second column. Column 33. An intermediate liquid 41 is passed from the first column 31 to the second column 33. Bottle liquid 65 of the first column is pressurized by a pump 67 and divided in two. Part of the liquid 69 may be sent as a product to the outside. The remainder 71 is sent to the vaporizer-condenser 35 at the top of the first column 31. The gas produced by vaporization 51 is sent in normal operation entirely to the tank of the second column33. Liquid oxygen 81 is withdrawn from the space around the vaporizer 35, pressurized and vaporized in the exchanger 17. This liquid can be replaced by a flow of pressurized liquid nitrogen which vaporizes in the same exchanger. Liquid nitrogen 45 from the reflux from the first column is extracted as product. Residual nitrogen 43 and nitrogen gas 49 are extracted at the top and bottom of the minaret of the second column 33. The presence of the minaret is not essential if pure nitrogen is not required.
    [0009] Nitrogen gas is not necessarily withdrawn at the top of the medium pressure column 31 One of the turbines 19,21 drives the cold booster 15 and the other drives the hot booster 13. It is therefore possible to regulate the compression ratio of the cold booster 15 by changing the air flow expanded in the turbine that drives the cold booster 15. If less air is expanded in the turbine, the associated work reduces and therefore the energy transmitted to the cold booster also reduces. In this way, the compression ratio of the cold booster can be reduced. Likewise by increasing the expanded flow rate in the turbine, the compression ratio can be increased.
    [0010] If the compression ratio has reduced beyond a permitted rate, for example reduced from 1.8 to 1.6, the process must be modified to allow continued operation. According to the invention, in this case, a portion 55 of the oxygen gas 51 vaporized by the vaporizer 35 is withdrawn from the column system through a valve 57 and is heated in the heat exchanger 17. To avoid complicating the exchanger, it may be mixed previously with another flow, for example, the flow 43 of residual nitrogen to form a flow 59. Thus the amount of gaseous oxygen 55 withdrawn goes from zero, when the compression ratio is sufficient raised to a few percent of the oxygen gas flow product 81, when the compression ratio is at least permissible, even exploiting the invention.
    [0011] The detection of the compression ratio is preferably done by measuring the flow rate of the air expanded in the turbine coupled to the cold booster, since the flow rate expanded in the turbine determines the compression ratio of the cold booster. On the other hand, other ways of detecting the compression ratio can be used, for example to measure the air pressure upstream and downstream of the cold booster, and to adjust the oxygen gas flow rate 55 as a function of the ratio between these two pressures. By withdrawing gaseous oxygen from the column system (flow rate 55) when the compression ratio of the cold booster goes below a threshold (for example below 60% of its nominal compression ratio or even below 85% of its nominal rate), this makes it possible to increase the production of possible liquid as final product with a single main exchange line and a single main air compressor. Part of the separation and compression energy of the products is transferred to a liquefaction energy.
    [0012] Thus with a compression ratio of the cold booster of 1.8, the liquefaction capacity is 1000 Nm3 / h. If the compression ratio decreases to 1.6, less oxygen gas is produced, 81 but the liquefaction capacity increases to 1500 Nm3 / h. According to another variant of the invention, as illustrated in FIG. 3, it is possible to use two cold boosters in series. The air is compressed, cooled and purified in the same way as for Figure 1 in a compressor 3 at a pressure between 12 and 30 bar abs before being divided into two. A part 9 is cooled in a heat exchanger 17 to an intermediate temperature thereof, supercharged in a first cold booster 13 and then supercharged in a second cold booster 15 and cooled again in the heat exchanger 17 before to be sent to distillation. Intermediate cooling between the two cold boosters 13,15 in the exchange line is optional. The other part 11 is cooled to an intermediate temperature of the exchanger 17. At this temperature, the portion 11 is divided in two. Each portion 23,25 is sent to a respective turbine 25,23 and the expanded flow rates are mixed to form a flow rate to be distilled 27. It is possible to consider pushing the total compression ratio of the cold boosters to more than 4, the rate compression defined as the ratio between the air pressure entering the first booster on the pressure of the air leaving the last booster. In the case of FIG. 3, the method can operate in a nominal operation with the two cold boosters 13, 15 in working order and the short-circuiting duct 71 closed by means of the valve 73. In this case, the product is produced oxygen gas at high pressure by vaporizing liquid oxygen pressurized in the exchanger 17 by heat exchange with the air. Due to the high compression ratio due to the two cold compressors in series, it is possible to operate with a lower pressure for the output of the main compressor 3 and thus a reduced energy consumption. In another step of the apparatus, the cold booster 15 does not work and the supercharged air passes from the outlet of the cold booster 13 via the pipe 71 and the open valve 73 to the heat exchanger 17 at lower pressure than during normal walking. To compensate for the reduction in compression ratio, since only a booster operates, oxygen gas is withdrawn from the column system and heats up in the heat exchanger 17, while there is no withdrawal of this kind during normal walking. The production of gaseous oxygen by vaporization is reduced, for example by 10%, but the production of liquid as final product is increased.
    [0013] The fact that the cold booster 15 is not working may be the result of a failure or less than optimal operation or otherwise may result in a voluntary step. According to the voluntary approach, it is decided to stop the cold booster, to allow a march with production of gaseous oxygen directly withdrawn from the low pressure column.
    [0014] For some air separation devices, the production of gas in operation is sometimes 80-85% of that for which the device is designed. According to the invention, this unnecessary gaseous production can be "spoiled" by sending it to air through line 55 (or other) to produce more liquid, while operating at the optimized operating point of the MAC HP.
    [0015] It also helps to react to customer peaks. In case of peak consumption of the customer, we can vaporize the stored liquid to complete the productions. We will not dimension the device on a maximum production size but on an intermediate size, which reduces the cost of the device The sending of gaseous oxygen, withdrawn in gaseous form, to the air makes it possible to distribute the power the main compressor between compression energy and liquefaction energy Using a pipe to send oxygen gas to the air, this allows punctually to increase the liquid production in operation "cold booster with reduced compression ratio". For all the figures, it is possible to operate by withdrawing a minimum flow rate of oxygen gas when the booster has a sufficient compression ratio. In this case, if the compression ratio of the booster or at least one of the boosters or boosters is above a threshold, a first rate of oxygen gas 55 is withdrawn equal to at most 2% of the gaseous product 81 The rate of compression of the booster or at least one of the boosters or boosters is below the threshold, a flow of oxygen gas 55 greater than the first flow is withdrawn from the column system and heats up in the heat exchanger 17.
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. A method of separating air by cryogenic distillation in which: i) air (1,7) is compressed at a first pressure, purified, cooled in a heat exchanger (17) and sent for separation in a vacuum system. columns (31,33) ii) at least a portion (9) of the purified air exits at an intermediate level of the heat exchanger, is supercharged in at least one booster (13,15), optionally in two series, having a variable compression ratio at an intermediate temperature of the heat exchanger, is returned to the heat exchanger to cool and is sent to the column system iii) a liquid flow is withdrawn from the column system, pressurized and vaporized in the heat exchanger to form a gaseous product (81) enriched in a component of air and a) if the compression ratio of the booster or at least one of the boosters or boosters is above a threshold, we do not withdraw it oxygen gas (55) of the column system and if the compression rate of the booster or at least one of the booster or booster is below the threshold, a flow of gaseous oxygen is withdrawn from the column system and heats up in the heat exchanger or b) if the compression ratio of the booster or at least one of the boosters or boosters is above a threshold, a first rate of gaseous oxygen equal to at most 2% of the gaseous product (81) rich in oxygen and is heated in the heat exchanger and if the compression ratio of the booster or at least one of the booster or booster is below the threshold, a flow of oxygen gaseous gas at the first flow rate is withdrawn from the column system and heats up in the heat exchanger.
    [0002]
    2. Method according to claim 1, wherein if the compression ratio of the booster or at least one of the booster or booster is above a threshold, no liquid is produced as the final product or a first quantity is produced. liquid (45, 69) as final product and if the decompression rate of the booster or at least one of the booster or booster is below the threshold, liquid is produced as the final product or a quantity of liquid is produced as a product. final greater than the first quantity.
    [0003]
    A process according to claim 1 or 2 wherein a nitrogen enriched flow (43) is withdrawn from the column system, the oxygen gas flow (55) is mixed with the nitrogen enriched flow to form a mixed flow (59). and the mixed flow is heated in the heat exchanger (17).
    [0004]
    4. Method according to one of the preceding claims wherein the oxygen gas flow (55) or the mixed flow (59) is sent to air.
    [0005]
    5. Method according to one of the preceding claims wherein only a portion (9) of the purified air is overpressed in the booster or the boosters (13,15) and another part (11) of the air is cooled in the heat exchanger (17) and expanded in a turbine coupled to the booster or in turbines (19,21) coupled to the boosters. 20
    [0006]
    6. The method of claim 5 wherein detecting the compression ratio of the booster or at least one of the boosters (13,15) by measuring the flow of air expanded in the turbine or turbines (19,21).
    [0007]
    7. Method according to one of the preceding claims wherein the air pressure is measured upstream and downstream of the booster or at least one of the boosters (13,15) to detect the compression rate of the booster. here or there.
    [0008]
    8. A process according to one of the preceding claims wherein an oxygen-rich gaseous product (81) is produced by withdrawing an oxygen-rich liquid from the column system (31,33) and vaporizing it in the heat exchanger. (17).
    [0009]
    9. The method of claim 8 wherein the flow of gaseous oxygen (55), withdrawn in case of compression ratio of the booster too low, is at most 10% of the gaseous product (81) rich in oxygen. 10
    [0010]
    An apparatus for separating cryogenic distillation air comprising a heat exchanger (17), a column system (31,33), at least one booster (15) having a variable compression ratio, a pipe for sending air air (27) compressed at a first pressure, purified and cooled from the heat exchanger to the column system for separation, means for outputting at least a portion (9) of the purified air at an intermediate level of the heat exchanger and to send it to the booster or series boosters (13,15) at an intermediate temperature of the heat exchanger, means for returning the pressurized air in the booster (s) to the booster. heat exchanger for cooling and being sent to the column system, a pipe for withdrawing a liquid flow from the column system, means for pressurizing the liquid flow and a pipe for sending the pressurized liquid flow to vaporize in the heat exchanger. ch to form a gaseous product (81) enriched in a component of air, characterized in that it comprises means for detecting the compression ratio of the booster or at least one of the boosters, means for withdrawing a debit gaseous oxygen system of the column system and means for varying the rate of oxygen gas (55) withdrawn from the column system as a function of the compression ratio (s) of the booster or at least one of the boosters.
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    同族专利:
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    引用文献:
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    US10359231B2|2017-04-12|2019-07-23|Praxair Technology, Inc.|Method for controlling production of high pressure gaseous oxygen in an air separation unit|
    FR3069913B1|2017-08-03|2020-06-26|L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude|APPARATUS AND METHOD FOR SEPARATING AIR BY CRYOGENIC DISTILLATION|
    EP3438585A3|2017-08-03|2019-04-17|L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude|Method for defrosting a device for air separation by cryogenic distillation and device adapted to be defrosted using this method|
    FR3069914B1|2017-08-03|2020-06-26|L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude|APPARATUS AND METHOD FOR SEPARATING AIR BY CRYOGENIC DISTILLATION|
    EP3870916A1|2018-10-26|2021-09-01|Linde GmbH|Method for obtaining one or more air products, and air separation unit|
    法律状态:
    2015-12-21| PLFP| Fee payment|Year of fee payment: 3 |
    2016-12-22| PLFP| Fee payment|Year of fee payment: 4 |
    2017-12-21| PLFP| Fee payment|Year of fee payment: 5 |
    2019-12-19| PLFP| Fee payment|Year of fee payment: 7 |
    2020-12-23| PLFP| Fee payment|Year of fee payment: 8 |
    2021-12-24| PLFP| Fee payment|Year of fee payment: 9 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1362152A|FR3014545B1|2013-12-05|2013-12-05|METHOD AND APPARATUS FOR AIR SEPARATION BY CRYOGENIC DISTILLATION|
    FR1362152|2013-12-05|FR1362152A| FR3014545B1|2013-12-05|2013-12-05|METHOD AND APPARATUS FOR AIR SEPARATION BY CRYOGENIC DISTILLATION|
    PCT/FR2014/053187| WO2015082860A2|2013-12-05|2014-12-05|Method and device for separating air by cryogenic distillation|
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