EP0399197B1 - Verfahren und Vorrichtung zur Tieftemperaturzerlegung von Luft - Google Patents

Verfahren und Vorrichtung zur Tieftemperaturzerlegung von Luft Download PDF

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Publication number
EP0399197B1
EP0399197B1 EP90106968A EP90106968A EP0399197B1 EP 0399197 B1 EP0399197 B1 EP 0399197B1 EP 90106968 A EP90106968 A EP 90106968A EP 90106968 A EP90106968 A EP 90106968A EP 0399197 B1 EP0399197 B1 EP 0399197B1
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EP
European Patent Office
Prior art keywords
oxygen
pressure stage
liquid
low
nitrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP90106968A
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German (de)
English (en)
French (fr)
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EP0399197A1 (de
Inventor
Wilhelm Rohde
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Linde GmbH
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Linde GmbH
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Publication of EP0399197A1 publication Critical patent/EP0399197A1/de
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04472—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using the cold from cryogenic liquids produced within the air fractionation unit and stored in internal or intermediate storages
    • F25J3/04496—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using the cold from cryogenic liquids produced within the air fractionation unit and stored in internal or intermediate storages for compensating variable air feed or variable product demand by alternating between periods of liquid storage and liquid assist
    • F25J3/04503—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using the cold from cryogenic liquids produced within the air fractionation unit and stored in internal or intermediate storages for compensating variable air feed or variable product demand by alternating between periods of liquid storage and liquid assist by exchanging "cold" between at least two different cryogenic liquids, e.g. independently from the main heat exchange line of the air fractionation and/or by using external alternating storage systems
    • F25J3/04509—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using the cold from cryogenic liquids produced within the air fractionation unit and stored in internal or intermediate storages for compensating variable air feed or variable product demand by alternating between periods of liquid storage and liquid assist by exchanging "cold" between at least two different cryogenic liquids, e.g. independently from the main heat exchange line of the air fractionation and/or by using external alternating storage systems within the cold part of the air fractionation, i.e. exchanging "cold" within the fractionation and/or main heat exchange line
    • F25J3/04515—Simultaneously changing air feed and products output
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
    • F25J3/04284—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams
    • F25J3/0429—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using internal refrigeration by open-loop gas work expansion, e.g. of intermediate or oxygen enriched (waste-)streams of feed air, e.g. used as waste or product air or expanded into an auxiliary column
    • F25J3/04303—Lachmann expansion, i.e. expanded into oxygen producing or low pressure column
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04406—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system
    • F25J3/04412—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air using a dual pressure main column system in a classical double column flowsheet, i.e. with thermal coupling by a main reboiler-condenser in the bottom of low pressure respectively top of high pressure column
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04642—Recovering noble gases from air
    • F25J3/04648—Recovering noble gases from air argon
    • F25J3/04654—Producing crude argon in a crude argon column
    • F25J3/04666—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system
    • F25J3/04672—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system having a top condenser
    • F25J3/04678—Producing crude argon in a crude argon column as a parallel working rectification column of the low pressure column in a dual pressure main column system having a top condenser cooled by oxygen enriched liquid from high pressure column bottoms
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
    • F25J2235/50—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being oxygen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S62/00—Refrigeration
    • Y10S62/912—External refrigeration system
    • Y10S62/913—Liquified gas

Definitions

  • the invention relates to a method and apparatus for the low-temperature separation of air with variable oxygen production, in which air is compressed, pre-cleaned, cooled and pre-separated in the pressure stage of a two-stage rectification into an oxygen-rich liquid fraction and a nitrogen fraction, and the oxygen-enriched liquid fraction into the low-pressure stage of the rectification , which is in heat-exchanging connection with the pressure stage, is introduced and further broken down into an oxygen and a nitrogen fraction and in which oxygen is removed from an oxygen tank when there is an increased demand for oxygen and liquid oxygen is fed from the low-pressure stage to the oxygen tank when the demand for oxygen is reduced.
  • Such a method is known for example from "LINDE reports from technology and science", 54/1984, pages 18-20.
  • the oxygen demand is subject to greater fluctuations over a period of minutes, hours or days. Because of the inertia of a low-temperature air separator, it would be uneconomical to adapt such a system by briefly changing the amount of air supplied and at the same time changing the sales in the rectification columns. Besides, one would have such a procedure has an unfavorable impact on the effectiveness of the separation process.
  • liquid oxygen is supplied to the bottom of the low-pressure stage from the oxygen tank and is evaporated there in the heat exchange with pressurized nitrogen at the top of the pressure stage. Nitrogen is liquefied during the heat exchange, removed from the pressure stage and stored in the nitrogen tank. At times when excess gaseous oxygen is produced, the stored liquid nitrogen is then available as a return in the low pressure column; Excess oxygen is removed from the bottom of the low-pressure column and stored in the oxygen tank.
  • the amount of additional oxygen that can be removed is set by the amount of pressurized nitrogen which is drawn off in gaseous form under normal load.
  • This part of the nitrogen generated in the pressure stage is generally not fed into the low-pressure stage, but is removed from the process, either directly as a gaseous product (under normal load and with reduced oxygen demand) or through intermediate storage in the nitrogen tank (with increased oxygen demand). Regardless of the current load, this amount of nitrogen is not available as a return for the low pressure stage.
  • the object of the invention is now to develop a method which enables variable oxygen production with cheaper product yields, in particular with an attached argon rectification.
  • This object is achieved in that when there is an increased oxygen requirement, the conversion in the pressure stage is increased and at least part of the oxygen-enriched liquid fraction is introduced into a liquid air tank and stored there, and in that when the oxygen requirement is reduced, the conversion in the pressure stage is reduced and oxygen-enriched liquid fraction from the liquid air tank removed and fed to the rectification.
  • the intermediate storage of sump liquid from the pressure stage according to the invention permits an operation of the system in which, on the one hand, the reflux conditions in the pressure and low pressure stage and the conversion in the low pressure stage can be kept constant, on the other hand, all nitrogen generated in the pressure stage can be withdrawn in liquid and the Low pressure stage are supplied. This provides the optimal amount of reflux for the low pressure rectification, the maximum achievable argon concentration is achieved.
  • the amount of air supplied is increased when there is an increased demand for oxygen.
  • This causes the desired increase in column turnover and thus the evaporation of the liquid additionally introduced from the oxygen tank into the sump of the low-pressure column.
  • the air supply is throttled and liquid is removed from the liquid air tank and the nitrogen tank in order to keep the sales in the low pressure column constant. Due to the lower conversion at the top of the pressure stage, a smaller part of the oxygen accumulating in the low pressure column is evaporated. The corresponding amount is drawn off in liquid form and stored in the oxygen tank.
  • the process according to the invention is advantageously controlled such that both the reflux ratio and the conversion in the low-pressure stage are kept essentially constant in the event of fluctuations in the amount of oxygen produced.
  • the return ratio also remains constant in the pressure stage.
  • an argon-containing oxygen fraction can be taken from the middle area of the low-pressure stage and in one Raw argon rectification can be broken down into raw argon and into a residual fraction.
  • the invention further relates to a device for carrying out the method described above with a two-stage rectification column which consists of a pressure column and a low pressure column with a common condenser / evaporator, a nitrogen tank which is connected to the pressure and low pressure column by means of nitrogen lines, and with an oxygen tank , which is connected to the low pressure column by means of oxygen lines.
  • the device according to the invention is characterized by a liquid air tank, a first liquid air line between the sump of the pressure column and the liquid air tank and a second liquid air line which connects the liquid air tank and the low pressure column.
  • the device has measuring devices for the liquid level in the pressure column and low-pressure column sump, a flow measuring device in the nitrogen line between the pressure column and nitrogen tank, throttle devices for controlling the flow in liquid air, oxygen and nitrogen lines and control devices which are compatible with the Measuring devices are connected and control the throttle devices.
  • the figure shows this variant of the method according to the invention in a schematic sketch.
  • Air is drawn in by an air compressor 1, then pre-cooled and cleaned (2) and passed via line 3 through a main heat exchanger 4, in which it is cooled in countercurrent to product gases. 70 to 95%, preferably 88%, of the air becomes cold End of the main heat exchanger 4 and fed via line 5 at a temperature of 95 to 105K and under a pressure of 4 to 8 bar into the pressure stage 10 of a two-stage rectification 9.
  • the remainder of the air is led out of the main heat exchanger 4 via line 6 at a temperature of 130 to 190 K, expanded to a pressure of 2.0 to 1.1 bar in an expansion turbine 7 and fed to the low pressure stage 11 of the rectification 9.
  • the air introduced via line 5 is broken down into liquid nitrogen and into an oxygen-enriched bottom liquid. Both fractions are withdrawn in liquid form, the nitrogen via line 14 and the bottom liquid via line 12.
  • the nitrogen is expanded using valve 134 and fed into a nitrogen tank which stores liquid nitrogen under a pressure of 1 to 6 bar.
  • the liquid is at least partially passed on via line 37, subcooled in a heat exchanger 23 and applied via line 15 to the top of the low-pressure stage 11.
  • the bottom liquid in line 12 is also depressurized (valve 132) and introduced into a liquid air tank 40 in which pressure conditions similar to those in the nitrogen tank 35 prevail. Liquid is removed from the tank 40 via line 42, cooled in the heat exchanger 23 and introduced into the low-pressure stage 11 via line 13b. There the oxygen-enriched liquid from pressure stage 10 is further broken down.
  • low-pressure stage 11 gaseous oxygen is taken off above the sump via line 16 and warmed to almost ambient temperature in main heat exchanger 4 (line 19).
  • nitrogen is drawn off at the top via line 18, heated in heat exchanger 23 against the liquid fractions 37 and 42 from the pressure stage 10 or from the tanks 35, 40, passed through line 19 through the main heat exchanger 4 and continues there except for im essential ambient temperature warmed.
  • liquid oxygen can be withdrawn from the bottom of the low-pressure stage 11 by means of the pump 31 and introduced into an oxygen tank 32.
  • liquid can be fed from the oxygen tank 32 into the low-pressure column 11 via line 34.
  • an argon-rich oxygen fraction is drawn off from the low pressure stage 11 via line 20, fed to a crude argon rectification 21 and there in crude argon, which is withdrawn via line 22 at the top of the crude argon rectification 21, and into one liquid residual fraction that over Line 20 flows back into the low pressure stage 11, disassembled.
  • the head of the crude argon rectification 21 is cooled by liquid from the bottom of the pressure column 10 or from the liquid air tank 40.
  • a secondary line 24 branches off from line 42 and leads into the top condenser 45 of the crude argon rectification 21.
  • the oxygen-enriched air evaporated there is drawn off via line 46 and via line 13a somewhat below the feed point of the liquid fraction (line 13b) into the low-pressure stage 11 introduced.
  • an increased flow is set on the air compressor 1.
  • the flow rate is monitored by the measuring device 125, which is connected to the air compressor 1 (line shown in broken lines in the figure).
  • the flow through line 6 via the expansion turbine 7 to the low-pressure stage 11 is kept essentially constant by controlling the flow through the expansion turbine 7 in accordance with the values indicated by the measuring device 127 (see dashed line in the drawing).
  • the amount of air additionally sucked in by the air compressor 1 is thus practically completely introduced into the pressure stage 10 and increases the column turnover there. For example, to remove a 25% increase in the amount of gaseous product oxygen, the total amount of air must be increased by approximately 6.8%.
  • the increased conversion in the pressure stage 10 now causes an increased heat input via the condenser / evaporator 48 into the bottom of the low pressure stage 11.
  • the additionally evaporated oxygen can be drawn off via line 16 as an increased amount of product. This process is controlled by the flow meter 126 and valve 136 in line 17.
  • a quantity of liquid oxygen corresponding to the additionally removed oxygen gas is removed from the oxygen tank 32 (line 34).
  • the replenishment of liquid oxygen is controlled by means of the liquid level measurement 123 at the bottom of the low pressure stage 11 and the valve 133.
  • the pressure in the liquid tanks 32, 35, 40 is monitored by means of measuring devices 101, 102, 103. If necessary, gas is released from tanks 32, 35, 40 by opening valves 111, 112 and 113, from liquid air tank 40 via lines 41 and 13a to the low pressure stage, from oxygen tank 32 via line 33 into product line 17 and from the nitrogen tank 35 via line 36 into the product line 19.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treatment Of Sludge (AREA)
  • Processing Of Solid Wastes (AREA)
EP90106968A 1989-04-27 1990-04-11 Verfahren und Vorrichtung zur Tieftemperaturzerlegung von Luft Expired - Lifetime EP0399197B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90106968T ATE77687T1 (de) 1989-04-27 1990-04-11 Verfahren und vorrichtung zur tieftemperaturzerlegung von luft.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3913880 1989-04-27
DE3913880A DE3913880A1 (de) 1989-04-27 1989-04-27 Verfahren und vorrichtung zur tieftemperaturzerlegung von luft

Publications (2)

Publication Number Publication Date
EP0399197A1 EP0399197A1 (de) 1990-11-28
EP0399197B1 true EP0399197B1 (de) 1992-06-24

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EP90106968A Expired - Lifetime EP0399197B1 (de) 1989-04-27 1990-04-11 Verfahren und Vorrichtung zur Tieftemperaturzerlegung von Luft

Country Status (13)

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US (1) US5084081A (cs)
EP (1) EP0399197B1 (cs)
JP (1) JP3048373B2 (cs)
AT (1) ATE77687T1 (cs)
AU (1) AU627869B2 (cs)
CA (1) CA2015458C (cs)
CZ (1) CZ277911B6 (cs)
DE (2) DE3913880A1 (cs)
ES (1) ES2033556T3 (cs)
HU (1) HU207154B (cs)
RU (1) RU1838732C (cs)
UA (1) UA19155A (cs)
ZA (1) ZA903182B (cs)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2647934A1 (de) 2012-04-03 2013-10-09 Linde Aktiengesellschaft Verfahren und Vorrichtung zur Erzeugung elektrischer Energie

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JP3048373B2 (ja) 2000-06-05
JPH0363490A (ja) 1991-03-19
HUT54310A (en) 1991-02-28
ATE77687T1 (de) 1992-07-15
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CA2015458C (en) 1998-09-29
EP0399197A1 (de) 1990-11-28
CA2015458A1 (en) 1990-10-27
AU627869B2 (en) 1992-09-03
HU902576D0 (en) 1990-08-28
US5084081A (en) 1992-01-28
AU5398390A (en) 1990-11-01
ZA903182B (en) 1991-04-24
CS9002111A2 (en) 1991-08-13
ES2033556T3 (es) 1993-03-16
DE3913880A1 (de) 1990-10-31
RU1838732C (ru) 1993-08-30
DE59000177D1 (de) 1992-07-30
CZ277911B6 (en) 1993-06-16
UA19155A (uk) 1997-12-25

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