CN1646869A - Method for extracting argon by low-temperature air separation - Google Patents

Method for extracting argon by low-temperature air separation Download PDF

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Publication number
CN1646869A
CN1646869A CNA038082780A CN03808278A CN1646869A CN 1646869 A CN1646869 A CN 1646869A CN A038082780 A CNA038082780 A CN A038082780A CN 03808278 A CN03808278 A CN 03808278A CN 1646869 A CN1646869 A CN 1646869A
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China
Prior art keywords
argon
column
fluid
segmentation
air separation
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CNA038082780A
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Chinese (zh)
Inventor
赖因哈德·格拉特哈尔
克里斯蒂安·孔茨
哈拉尔德·兰克
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Linde GmbH
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Linde GmbH
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Priority claimed from DE2002116269 external-priority patent/DE10216269A1/en
Application filed by Linde GmbH filed Critical Linde GmbH
Publication of CN1646869A publication Critical patent/CN1646869A/en
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/141—Fractional distillation or use of a fractionation or rectification column where at least one distillation column contains at least one dividing wall
    • 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
    • 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
    • F25J3/04703—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 being arranged in more than one vessel
    • 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
    • F25J3/04709—Producing crude argon in a crude argon column as an auxiliary column system in at least a dual pressure main column system
    • 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
    • F25J3/04763—Start-up or control of the process; Details of the apparatus used
    • F25J3/04866—Construction and layout of air fractionation equipments, e.g. valves, machines
    • F25J3/04896—Details of columns, e.g. internals, inlet/outlet devices
    • F25J3/04933—Partitioning walls or sheets
    • F25J3/04939—Vertical, e.g. dividing wall columns
    • 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
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/34—Processes or apparatus using separation by rectification using a side column fed by a stream from the 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
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/10—Mathematical formulae, modeling, plot or curves; Design methods
    • 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
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/12—Particular process parameters like pressure, temperature, ratios

Abstract

The invention relates to a method for extracting argon by low-temperature air separation. To this end, the rectifying system (2, 4) comprises at least one air separation column (4) subdivided into a first and second partial section (6, 7) by a partition (5) extending in a longitudinal direction of the column. A fluid (3) containing oxygen and argon is introduced into the first partial section (6), and a flow (13) containing oxygen and argon and having an argon concentration ranging from 15 % to 50 % is withdrawn from the second partial section (7).

Description

Be used for obtaining the method for argon by Cryogenic air separation
The present invention relates to a kind of being used for by obtain the method for argon at a distillation system low temperature air separating, this distillation system has the rectifying section that three series connection are settled, wherein, the first and second and second and the 3rd rectifying section respectively aspect gas and the liquid aspect interconnect, and, second rectifying section has two segmentations, they aspect gas and the liquid aspect do not interconnect and flow through side by side, wherein, input contains the fluid of aerobic and argon in first segmentation in two segmentations, extracts the fluid that contains aerobic and argon in second segmentation from two segmentations.
The boiling point of argon is between the boiling point of oxygen and nitrogen.When traditional employing two stage rectification low temperature air separating, argon enrichment in the zone line of lower pressure column.In order to obtain argon, from this zone, extract the gaseous fraction of mainly forming usually by oxygen and argon.This enriched fraction that contains 10% argon of having an appointment is transfused to so-called crude argon column, and the rectifying of carrying out oxygen and argon therein separates.Can extract argon at the crude argon column top, gathered main oxygen containing liquid in its liquid pool, these liquid are back in the lower pressure column.
Usually require argon purity more than 95% in practice.But the fluid that in known method, only contains 10% argon of having an appointment to the crude argon column input.In order it to be concentrated to desired high argon purity and to extract desirable product volume at the crude argon column top, must be with a large amount of steam input crude argon columns and in its inside rectifying.The cross section of crude argon column must be selected corresponding greatly, therefore can produce very big investment cost.
Particularly from the technical field of obtaining hydrocarbon, know, use so-called partition-wall column to be used for separation of tertiary mixture.In a partition-wall column, the part of tower is divided into two segmentations by a wall of settling on the tower longitudinal direction.This above dividing wall and below, these two segmentations connect aspect flowing respectively.When adopting suitable method of operating, the interior ternary mixture of segmentation that flow into dividing wall one side is separated into three kinds of cuts in a unique tower.The component of easy boiling can be obtained at the top of partition-wall column, and the component of medium boiling is obtained at the dividing wall opposite side opposite with input side, and the component of difficult boiling is obtained from liquid pool.Compare with the tower that does not have dividing wall, the medium boiling component that side is extracted on the mouth by partition-wall column reaches higher concentration.
In Cryogenic air separation, almost do not adopt partition-wall column up to now, because it is difficult to regulate.In EP 0 638 778 B1, introduced a kind of in partition-wall column the method for low temperature air separating.Lower pressure column is separated by a dividing wall in the zone therebetween.At the liquid pool liquid of a side of dividing wall input, and extract the fluid that contains argon out at the opposite side of dividing wall from pressure column.In order to improve the adjusting of this method, go out waste fluid at a side-draw of the input liquid pool liquid of dividing wall.Technological parameter is selected like this, makes the argon fluid that contains that obtains have minimum 70% argon concentration.
When the argon concentration that requires product is in 70% scope, adopt the method for introducing among EP 0 638 778 B1 can reduce interior theoretical cam curve of crude argon column and saving building height.If but required for example high argon concentration more than 95%, the advantage that then will be concentrated to 70% above argon from the fluid that lower pressure column proposed and flowed to crude argon column would just become more and more littler.This be because, in order to reach high argon concentration, must have a plurality of theoretical trays to be used for removing the oxygen of final degree in the crude argon column from argon.That is to say that when purity requirement was high, the initial concentration of the fluid in the input crude argon column only played small effect.
Therefore, task of the present invention is to provide a kind of being used for to obtain improving one's methods of argon by Cryogenic air separation.
According to the present invention, this task solves by the method for the described type of beginning, and wherein, the argon concentration in the fluid that obtains from second segmentation is 15% to 50%, preferably between 15% to 40%, between 20% to 35%.
The present invention is based on such knowledge: when the amount of predesignating the argon product and purity, the initial concentration that improves the argon in the fluid in the input crude argon column brings the quantity of steam of conveying to reduce thereupon.With regard to the crude argon column cross section corresponding reduce and can cost saving with regard to, this is favourable.
But the argon concentration raising that the side of air separation is extracted on the mouth makes that the complex structure of air separation and adjusting are bothersome.To note in addition, it is more and more littler to extract the advantage that concentrates argon concentration on the mouth in the side of air separation when product requirement is high, because introduce as top, in this case, theoretical cam curve in the crude argon column depends primarily on the ultimate density that will reach, and does not depend on initial concentration.
Studies show that now, must import the increase that minimum steam in the crude argon column measures earlier along with argon concentration and descend in order to reach normal function, still, is 50% to keep identical from argon concentration.That is to say that side is extracted and mouthful to be gone up further argon and concentrate and reach 50% quantity of steam that can not continue to reduce when above in the input crude argon column, so does not have possibility to continue to reduce the cross section of crude argon column.Only kept argon concentration advantage of higher in the mixture in the input crude argon column.But because the theoretical cam curve in the crude argon column does not depend on initial concentration substantially when requiring argon purity high, so the argon concentration that continue to improve in the fluid that obtains from air separation no longer includes meaning.Within the scope of the present invention, this fact has been carried out studying in great detail and determined that argon purity is particularly advantageous in the fluid that obtains from second segmentation 15% to 50%.
Show in practice, when the argon concentration the fluid that obtains from second segmentation between 15% and 40%, preferably between 20% and 35% the time, this method is particularly advantageous.
The present invention is particularly advantageous when using partition-wall column.In this case, distillation system has at least one air separation, and it has the rectifying sections that three series connection are settled, wherein, rectifying section adjacent one another are respectively aspect gas and the liquid aspect interconnect.Middle rectifying section has a dividing wall, and this dividing wall is divided into two segmentations with rectifying section.In second rectifying section, stop two gas exchange and fluid exchange between the segmentation by this dividing wall.But two segmentations be positioned at top be positioned at following rectifying section and be connected aspect flowing.
Replace partition-wall column, also can be divided into two segmentations of being crossed by two towers of settling that are parallel to each other by concurrent flow.Extract liquid and flow to one second tower from a middle part of one first air separation.Gas is drawn and is entered in second tower from one second middle part of first air separation.The gas that produces on the top of second tower and be preferably on these two middle parts from the liquid of the liquid pool of second tower is back in first air separation.In this structure, two segmentations that separate aspect flowing are not by a dividing wall but realize by the tower of two parallel connections.
The fluid that goes out from second stage extraction preferably is transfused to the crude argon column, and this fluid takes out according to structure or from air separation or takes out from second tower.Accumulate in the there, main oxygen containing liquid pool liquid preferably is back in second segmentation, that is to say, be back to that and therefrom also extract and contain in the segmentation of argon cut.
The present invention preferably is applicable to the distillation system with a pressure column and a lower pressure column, and wherein, dividing wall is placed in the lower pressure column, and from the oxygen-rich fluid of pressure column, particularly liquid pool liquid is transfused in first segmentation.
Particularly when in crude argon column, obtain purity more than 95%, preferred high-purity argon and/or oxygen content more than 98% be lower than 100ppm, when preferably being lower than the argon of 10ppm, the inventive method shows to have advantage.If in crude argon column, use more than 100, the preferred theoretical tray between 150 to 200, advantageous particularly then of the present invention.In these cases, the structure height of crude argon column is always decided by the high desired theoretical cam curve of final purity.But, to compare with the conventional method that does not have partition-wall column, the diameter of crude argon column can obviously reduce.
Be preferably in and insert the filler that is used for rectifying in the air separation.At this advantageously, these fillers are placed in a plurality of stacked up and down zones, in the promptly so-called bed, wherein, the liquid of rectifying and/or want the gas of rectifying to be collected between per two beds and quilt is redistributed on the next packed bed.If replace filler to use other built-in fittings or device to be used for rectifying in air separation, same suitable is mutually gatherer and/or distributor to be set across a certain distance in air separation, so that can resist the skewness in the tower.
Dividing wall between two zones that are spaced in air separation is preferably stopping on the upper end of a packed bed or on the lower end respectively, perhaps when using other built-in fittings on the upper end at respective regions or stop on the bottom, this zone is separated by a collector/distributor and adjacent area.Because the joint in two tower zones is settled collector/distributor always, so when introducing dividing wall, other collector/distributor needn't be set.Have only the collector/distributor that directly is placed in dividing wall top to be reequiped, make it in the way you want with liquid distribution to two by in the dividing wall segmentation spaced apart from each other.If it is replace partition-wall column to use one to be parallel to second tower that first air separation is settled, corresponding therewith.
Proof is particularly advantageous at this is that the lower pressure column in air separation, the particularly two-column plant is divided into four zones, be divided into four packed beds under the situation of using filler, and dividing wall is arranged on the height in the second and the 3rd zone.
The mass transfer component of in first and second segmentations, preferably packing into the gas effect uniform pressure that rises being fallen.
Introduce the present invention and other details of the present invention in detail by embodiment illustrated in the accompanying drawings below.Shown in the figure:
Fig. 1 is used to implement a device of the inventive method,
Fig. 2 another form of implementation of the present invention,
Fig. 3 imports the interior unit quantity of steam of crude argon column and the dependence of its argon concentration,
The dependence of the argon concentration in the steam in Fig. 4 argon output and the input crude argon column.
The rectifying part that can obtain the low temp air fractionation system of argon shown in Figure 1.Input air 1 is imported in the pressure column 2 after corresponding purification and cooling.The interior oxygen enriched liquid of liquid pool that accumulates in pressure column 2 is imported in the lower pressure column 4 by pipeline 3.
Lower pressure column 4 constitutes partition-wall column.Be provided with filler as the rectifying element in lower pressure column 4, they are placed on a plurality of stacked up and down beds 19,20,21,22, and these have about 6 meters height respectively.Between per two beds, be provided be used to collect and the lower pressure column 4 that distributes in the collector/distributor 23,24,25,26,27 of the liquid that flows downward.
In the zone line of lower pressure column 4, settle a dividing wall 5 like this, made lower pressure column 4 be divided into two segmentations 6,7.At this, dividing wall 5 extends on the total length of packed bed 20 in the middle of two and 21.Gas exchange and fluid exchange can not take place between two segmentations that are spaced 6,7 in this zone.
On the contrary, below the segmentation 6,7 that is spaced and above bed 19 and 22 on the entire cross section of lower pressure column 4, extend, cause that gas stream separated rising and that descend and liquid stream are gathered together again in two segmentations 6,7.
In the segmentation 6 that is spaced, liquid pool liquid is input to the lower pressure column 4 from pressure column 2 by pipeline 3.Can the turbine air be imported in the lower pressure column 4 by pipeline 12 for this reason.On the top of lower pressure column 4, can obtain the nitrogen product of gaseous state by pipeline 8.In addition, above the segmentation 6,7 that is spaced, be provided with one and be used for the not extraction mouth 9 of purity nitrogen.Can obtain gaseous state or liquid oxygen product from the liquid pool of lower pressure column 4 by pipeline 10 and 11.
Packed in two segmentations 6 and to have had the filler of identical specific area with 7.Like this, the steam that rises in lower pressure column suffers the identical pressure loss in two segmentations 6,7.The liquid thereby that flows downward helps distributor 24,25 and is distributed in two segmentations 6,7.Especially in two segmentations 6,7, offer identical amount of liquid.But for method optimization, it is significant fully that different liquid handling capacities is set in segmentation 6 and 7.It is favourable that the steam that makes rising is distributed to according to the amount of liquid of counter current and the pressure losses in the packed bed 20,21 that yes in two segmentations 6,7.
From segmentation 7, extract mainly contain argon and oxygen, argon concentration is 35% fluid 13 and is transported to one and is provided with in the Packed crude argon column 14.This oxygen-argon mixture of rectifying in crude argon column 14.At the top of crude argon column 14, the argon that is produced condensation in an evaporator overhead condenser 15, a part is acquired as the product 16 that the residue oxygen content is lower than 10ppm, and a part 17 is sent back to again on the crude argon column 14 as withdrawing fluid.Liquid oxygen accumulates in the liquid pool of crude argon column 14, is back to by pipeline 18 in the segmentation that is spaced 7 of lower pressure column 4.
In lower pressure column 4, will separate with argon extraction mouth 13 from the liquid pool liquid 3 and the turbine air 12 of pressure column 2 by dividing wall 5.Adopt this mode, obviously higher in the argon concentration ratio that argon extracts generation in mouthfuls 13 is not having the tower of dividing wall.
Figure 2 illustrates a form of implementation of the present invention, in this form of implementation, be provided with a parallel other tower 30 and replace dividing wall 5.Components identical is indicated with identical mark in two accompanying drawings.
In this case, lower pressure column 4 does not have dividing wall.The liquid thereby that flows down from rectifying section 22 helps distributor 24 and is distributed on the bed 20,21 that constitutes first segmentation.Second segmentation realizes by this side tower 30.The part of the liquid that flows down from packed bed 22 is discharged from lower pressure column 4 and is transported to by pipeline 31 on the top of other tower 30.Above packed bed 21, be back in the lower pressure column 4 by pipeline 32 at the gas that produces on the top of other tower 30.Correspondingly, by pipeline 33 liquid is transported in the lower pressure column 4 and by pipeline 34 from other tower 30 gas is transported in the other tower 30 from lower pressure column 4.
Process is identical in form of implementation illustrated in figures 1 and 2, wherein just represents first segmentation 6 at the rectifying section 20,21 of Fig. 2 mesolow tower 4, and other tower 30 is represented second segmentation 7.Correspondingly, fluid 3,12 is imported in the lower pressure column 4, and the fluid 13 that contains argon is extracted from other tower 30.
Within the scope of the present invention, by simulating to determine the unit quantity of steam in the input crude argon column 14, that is to say the quantity of steam relevant according to the argon concentration of steam with the argon product volume.Figure 3 illustrates the dependence of obtaining.At this, with the argon product purity be 98.5% and argon output constant rate constant, that is to say the argon amount in argon product and the input air be starting point.
Real curve shows the theoretical minimum quantity of steam when unlimited theoretical cam curve.It is the 50 curve trends of calculating that empty curve shows at theoretical cam curve.Two curves have essentially identical trend.Yet, from curve, learn at the limited number of plates, compare with theoretical curve in this case to import and have more about quantity of steam of 30% to 40%.
Two curves show, at first along with argon concentration improves must be with in the steam input crude argon column 14 less and less so that obtain the argon of the purity that requires and amount.But, these curves argon concentration be about 50% o'clock approaching with a low extreme value respectively.What can expect when argon concentration is higher is that the quantity of steam that will import does not have or only a little also continue to descend.
When the argon concentration in the fluid that is supplied to crude argon column 14 improved, quantity of steam reduced, and therefore, the diameter of crude argon column can be correspondingly less.Yet what see is, the minimizing of quantity of steam is till about 50% o'clock to argon concentration only.On the contrary, bring up to 50% when above, under having ready conditions, can not continue to reduce quantity of steam, so just can not continue to reduce the cross section of crude argon column when argon concentration.Yet the lower pressure column expense of regulating that occurs along with the concentration raising obviously increases.
Product purity in hope is 98.5% o'clock, theoretical cam curve in the crude argon column 14 can not reduce by improving the argon concentration in the steam 13 that will import greatly yet, because the number of plates is by the ultimate density decision that will reach when product purity is high, rather than determine by initial concentration.
According to the present invention, lower pressure column 4 is worked like this, and the argon concentration that makes side extract in the mouth 13 reaches 45%.When this concentration, be input to diameter and the quantity of steam that quantity of steams in the crude argon column 4 drop to minimum and crude argon column 14 and correspondingly reduce.
Figure 4 illustrates the argon output of the argon concentration in the steam that depends in the input crude argon column.Real curve has provided the value of calculating at a short dividing wall, and empty curve has provided the value of calculating at a long dividing wall.Wherein, the number of plates in the lower pressure column remains unchanged.
See that from the curve of reality argon output keeps constant substantially in the time of in the argon concentration of input in the steam is in 10% scope between 25%.This curve interrupted at 25% o'clock, because can not reach higher argon concentration along with dividing wall length increases.The calculating of imaginary curve is long based on dividing wall, at this, also be argon concentration be more than 30% to 90% the higher range definite substantially invariable argon output.Therefore, improving argon concentration can not have a negative impact to output.

Claims (13)

1, be used for by obtain the method for argon at a distillation system low temperature air separating, this distillation system has the rectifying section that three series connection are settled, wherein, first and second rectifying section and the second and the 3rd rectifying section respectively aspect gas and the liquid aspect interconnect, wherein, second rectifying section has two segmentations, they aspect gas and the liquid aspect do not interconnect and flow through side by side, wherein, input contains the fluid of aerobic and argon in first segmentation in these two segmentations, extract the fluid that contains aerobic and argon in second segmentation from these two segmentations, it is characterized by, the argon concentration in the fluid (13) that extracts from second segmentation (7,30) is between 15% to 50%, preferably between 15% to 40%, between 20% to 35%.
2, in accordance with the method for claim 1, it is characterized by, this distillation system has at least one air separation (4), the rectifying section (19 that it has three series connection to settle, 20,21,22), wherein, second rectifying section (20,21) have a dividing wall that extends (5) on the tower longitudinal direction, by this, air separation (4) is divided into one first segmentation (6) and one second segmentation (7) on the height of dividing wall (5).
3, in accordance with the method for claim 1, it is characterized by, this distillation system has at least one first air separation (4) and one second tower (30), they are being connected with the middle part of liquid aspect with first air separation (4) aspect the gas on upper and lower end, upper end, wherein, section (20,21) and second tower (30) between these middle parts of first air separation constitute described two segmentations.
4, in accordance with the method for claim 3, it is characterized by, from second tower (30), extract the fluid (13) that contains aerobic and argon.
5, according to the described method of one of claim 1 to 4, it is characterized by, the fluid (13) that takes out from second segmentation (7,30) is fed to a crude argon column (14).
6, in accordance with the method for claim 5, it is characterized by, turn back in second segmentation (7,30) from the liquid pool liquid of this crude argon column (14).
7, according to claim 5 or 6 described methods, it is characterized by, in crude argon column (14), obtain purity more than 95%, preferred argon more than 98%.
8, according to the described method of one of claim 5 to 7, it is characterized by, in crude argon column (14), obtain the argon that oxygen content is lower than 10ppm.
9, according to the described method of one of claim 5 to 8, it is characterized by, crude argon column (14) has more than 100, preferred 150 to 200 theoretical trays.
10, according to the described method of one of claim 1 to 9, it is characterized by, packing at least in part in rectifying section (19,20,21,22) is used for the filler of rectifying.
11, in accordance with the method for claim 10, it is characterized by, the fluid that contains aerobic and argon is collected between two rectifying sections respectively and/or distribute (23,24,25,26,27).
12, according to the described method of one of claim 1 to 9, it is characterized by, in distillation system, be gaseous state fluid that rise, that contain aerobic and argon and in first and second segmentations (6,7), suffer the same pressure loss.
13, according to the described method of one of claim 1 to 12, it is characterized by, this distillation system has a pressure column (2) and a lower pressure column (4), wherein, dividing wall (5) is placed in the lower pressure column (4), and, be transfused in first segmentation (6) from the fluid (3) of the oxygen enrichment of pressure column (2).
CNA038082780A 2002-04-12 2003-04-01 Method for extracting argon by low-temperature air separation Pending CN1646869A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE2002116269 DE10216269A1 (en) 2002-04-12 2002-04-12 Process for recovering argon from air in a rectification system using a low temperature decomposition method comprises removing a stream having a specified argon concentration from a partial section of a rectification section
DE10216269.7 2002-04-12
EP02011058 2002-05-17
EP02011058.1 2002-05-17

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CN106468498A (en) * 2015-08-20 2017-03-01 林德股份公司 For preparing distillation column system and the device of oxygen by low-temperature fractionation air
CN112955707A (en) * 2018-10-23 2021-06-11 林德有限责任公司 Method and apparatus for the cryogenic separation of air
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CN103748427A (en) * 2011-08-25 2014-04-23 林德股份公司 Method and apparatus for the low-temperature fractionation of a fluid mixture
CN103748427B (en) * 2011-08-25 2015-12-23 林德股份公司 For the method and apparatus of low-temperature fractionation fluid mixture
CN106468498A (en) * 2015-08-20 2017-03-01 林德股份公司 For preparing distillation column system and the device of oxygen by low-temperature fractionation air
CN106468498B (en) * 2015-08-20 2020-09-22 林德股份公司 Distillation column system and apparatus for producing oxygen by cryogenic fractionation of air
CN112955707A (en) * 2018-10-23 2021-06-11 林德有限责任公司 Method and apparatus for the cryogenic separation of air
CN112955707B (en) * 2018-10-23 2023-01-24 林德有限责任公司 Method and apparatus for the cryogenic separation of air
CN114923313A (en) * 2022-05-17 2022-08-19 陕西聚能新创煤化科技有限公司 Crude argon refining liquid argon system and refining process thereof
CN114923313B (en) * 2022-05-17 2024-02-09 陕西聚能新创煤化科技有限公司 Crude argon refining liquid argon system and refining process thereof

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RU2004133324A (en) 2006-01-27
EP1495274A1 (en) 2005-01-12
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AU2003229590A1 (en) 2003-10-27
WO2003087686A1 (en) 2003-10-23

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