KR940020083A - 공기분리 시스템으로부터 고회수율로 아르곤의 회수를 최대화하는 방법 - Google Patents
공기분리 시스템으로부터 고회수율로 아르곤의 회수를 최대화하는 방법 Download PDFInfo
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- KR940020083A KR940020083A KR1019940001673A KR19940001673A KR940020083A KR 940020083 A KR940020083 A KR 940020083A KR 1019940001673 A KR1019940001673 A KR 1019940001673A KR 19940001673 A KR19940001673 A KR 19940001673A KR 940020083 A KR940020083 A KR 940020083A
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- Prior art keywords
- argon
- feed stream
- column
- nitrogen content
- low pressure
- Prior art date
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000926 separation method Methods 0.000 title claims abstract description 6
- 229910052786 argon Inorganic materials 0.000 title claims abstract 23
- 238000011084 recovery Methods 0.000 title claims abstract 9
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000004821 distillation Methods 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract 12
- 238000005259 measurement Methods 0.000 claims abstract 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims 6
- 239000001301 oxygen Substances 0.000 claims 4
- 229910052760 oxygen Inorganic materials 0.000 claims 4
- 238000004364 calculation method Methods 0.000 claims 3
- 239000000203 mixture Substances 0.000 claims 2
- 238000004088 simulation Methods 0.000 claims 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 claims 1
- 238000004422 calculation algorithm Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 238000002474 experimental method Methods 0.000 claims 1
- 238000012417 linear regression Methods 0.000 claims 1
- 238000012544 monitoring process Methods 0.000 claims 1
- 238000010992 reflux Methods 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- 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
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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
- 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
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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
- F25J3/04763—Start-up or control of the process; Details of the apparatus used
- F25J3/04769—Operation, control and regulation of the process; Instrumentation within the process
- F25J3/04793—Rectification, e.g. columns; Reboiler-condenser
- F25J3/048—Argon recovery
-
- 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
- F25J3/04769—Operation, control and regulation of the process; Instrumentation within the process
- F25J3/04848—Control strategy, e.g. advanced process control or dynamic modeling
-
- 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
- F25J2215/00—Processes characterised by the type or other details of the product stream
- F25J2215/58—Argon
-
- 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
-
- 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
- Y10S62/923—Inert gas
- Y10S62/924—Argon
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명은 정류의 다중 정류단을 포함하는 고압 및 저압 증류컬럼 및 아르곤 회수를 위한 분리 분지컬럼을 가지는 공기분리 시스템으로부터 높은 아르곤 회수율로 아르곤 회수를 최대화하는 방법에 관한 것이다. 조성측정에 의해 공정을 플랜트 공정변화에 민감한 것으로 확인된 정류의 미리 선택된 하나 이상의 단에서 공정변수를 형성한다. 아르곤 공급물에서의 전체 질소함량은 이러한 조성측정으로부터 시뮬레이션된 수학적인 상관관계에 의해 계산될 수 있다.
Description
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
제 1 도는 본 발명에 따른 공정을 수행하기 위하여, 적합한 제어 루우프에 의해 산소부분, 질소부분 및 아르곤 부분을 생성하도록 세개의 증류컬럼을 가지는 공기분리 플랜트의 개략적인 도면.
Claims (14)
- 저압증류 컬럼내의 상승증기를 세척하기 위하여 질소부화 환류유체를 제공하는 고압컬럼을 가지는 정류의 다중 증류단을 포함하는 고압 및 저압증류 컬럼 및 아르곤 회수를 위한 분리 분지컬럼을 가지는 공기분리 시스템으로부터 높은 아르곤 회수율로 아르곤 회수를 최대화하는 방법으로서, a) 비교가능한 산소-질소 평형이 존재하는 공급지점에서 저압컬럼으로 산소부화 유체를 도입하는 단, b) 도입 공급기류로 사용하기 위해 아르곤 함량이 상대적으로 높은 위치에서 저압컬럼으로부터 아르곤 분지컬럼으로 유체 공급기류를 유도하는 단계, c) 공기분리 시스템내의 공정변화에 대하여 상대적으로 민감한 저압컬럼내 각 정류단을 공급지점과 공급기류 위치 사이에서 확인하는 단계, d) 아르곤 분지컬럼에 대한 도입 공급기류의 복합물을 모니터하기 위하여 공정변화에 민감한 것으로 확인된 정류단들 중에서 적어도 하나를 선택하는 단계, e) 선택된 정류단에서 저압컬럼내의 조성-변수와 공급기류내의 질소함량 사이의 관계를 정의하는 모델을 공식화하는 단계, f) 선택된 정류단에서 조성변수를 측정하는 단계, g) 측정된 조성 변수치에 의해 모델로부터 아르곤 분지컬럼으로 도입된 공급기류내의 질소농도를 계산하는 단계, 및 h) 도입된 공급기류내의 질소 계산치에 대하여 공정의 조작을 제어하는 단으로 구성되는 방법.
- 제 1 항에 있어서, 매우 민감한 적어도 두개의 정류단이 복합물 측정에 대해 선택되는 것을 특징으로 하는 방법.
- 제 2 항에 있어서, 다수의 정류단이 가장 민감한 위치의 적어도 약 80%를 이루도록 충분하게 선택되는 것을 특징으로 하는 방법.
- 제 2 항에 있어서, 산소부화 유체가 고압컬럼으로부터 유도되는 것을 특징으로 하는 방법.
- 제 4 항에 있어서, 온도가 선택된 정류단에서 측정된 조성변수인 것을 특징으로 하는 방법.
- 제 5 항에 있어서, 모델이 하기 알고리즘에 의해 각 선택된 단에서 아르곤 공급기류내의 질소 및 온도 사이의 관계를 한정하도록 하기와 같이 공식화 되는 것을 특징으로 하는 방법 ; N=(a)T[상기식에서, a는 실험에 의해 결정되는 상수이고, T는 정류의 선택된 단에서의 온도이다].
- 제 6 항에 있어서, 상기 아르곤 공급기류내의 전체 질소함량이 하기 수식에 의해 계산되는 것을 특징으로 하는 방법 ;Yn=(a)T1+(b)T2+(c)T3+…[상기식에서, Yn은 아르곤 공급기류내의 계산된 전체 질소함량이며, (a), (b) 및 (c)등은 a, b 및 c등의 해당 정류단에서 온도의 계수이다].
- 제 7 항에 있어서, 아르곤 공급기류가 다중 선형회귀를 이용하여 수학적인 시뮬레이션에 의해 계산되는 것을 특징으로 하는 방법.
- 제 8 항에 있어서, 공정이 가능한 최고 아르곤 회수의 10%내에서 조작되는 것을 특징으로 하는 방법.
- 제 7 항에 있어서, 아르곤 컬럼으로의 공급물 유속이 아르곤 공급기류내의 질소함량 계산에 대해 조정되는 것을 특징으로 하는 방법.
- 제 5 항에 있어서, 아르곤 컬럼으로의 공급물 유속이 선택된 정류단에서 온도변수에 대해 조정되는 것을 특징으로 하는 방법.
- 제10항에 있어서, 아르곤 공급기류에 대한 질소함량의 계산이 산소부화 유체의 유속제어를 위한 제어가 일어나는 아르곤 생성기류내의 질소함량 변화를 나타내는 제어신호와 비교되는 것을 특징으로 하는 방법.
- 제10항에 있어서, 아르곤 공급기류로의 질소함량 계산이 산소부화 유체의 흐름을 조절하기 위한 제어를 발생하기 위해 수동으로 설정된 설정지점과 비교되는 것을 특징으로 하는 방법.
- 제 6 항에 있어서, 모델이 열역학적 데이터 시뮬레이션 또는 조작 플랜트 데이터로부터 도식화 되는 것을 특징으로 하는 방법.※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/011,605 | 1993-02-01 | ||
US08/011,605 US5313800A (en) | 1993-02-01 | 1993-02-01 | Process for maximizing the recovery of argon from an air separation system at high argon recovery rates |
Publications (1)
Publication Number | Publication Date |
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KR940020083A true KR940020083A (ko) | 1994-09-15 |
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ID=21751160
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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KR1019940001673A KR940020083A (ko) | 1993-02-01 | 1994-01-31 | 공기분리 시스템으로부터 고회수율로 아르곤의 회수를 최대화하는 방법 |
Country Status (9)
Country | Link |
---|---|
US (2) | US5313800A (ko) |
EP (1) | EP0609814B1 (ko) |
JP (1) | JPH06241653A (ko) |
KR (1) | KR940020083A (ko) |
CN (1) | CN1092519A (ko) |
BR (1) | BR9400397A (ko) |
CA (1) | CA2114573A1 (ko) |
DE (1) | DE69402572T2 (ko) |
ES (1) | ES2101363T3 (ko) |
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US5313800A (en) * | 1993-02-01 | 1994-05-24 | Praxair Technology, Inc. | Process for maximizing the recovery of argon from an air separation system at high argon recovery rates |
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GB9405161D0 (en) * | 1994-03-16 | 1994-04-27 | Boc Group Plc | Method and apparatus for reboiling a liquified gas mixture |
US5431023A (en) * | 1994-05-13 | 1995-07-11 | Praxair Technology, Inc. | Process for the recovery of oxygen from a cryogenic air separation system |
US5522224A (en) * | 1994-08-15 | 1996-06-04 | Praxair Technology, Inc. | Model predictive control method for an air-separation system |
CA2192043A1 (en) * | 1995-12-05 | 1997-06-06 | Daniel C. Smith | Apparatus and method for cutting bagles |
US5925291A (en) * | 1997-03-25 | 1999-07-20 | Midwest Research Institute | Method and apparatus for high-efficiency direct contact condensation |
US5730003A (en) * | 1997-03-26 | 1998-03-24 | Praxair Technology, Inc. | Cryogenic hybrid system for producing high purity argon |
US5916261A (en) * | 1998-04-02 | 1999-06-29 | Praxair Technology, Inc. | Cryogenic argon production system with thermally integrated stripping column |
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FR2855872A1 (fr) * | 2004-06-25 | 2004-12-10 | Air Liquide | Appareil de distillation, procede et appareil de separation d'air par distillation cryogenique |
US7501009B2 (en) * | 2006-03-10 | 2009-03-10 | Air Products And Chemicals, Inc. | Combined cryogenic distillation and PSA for argon production |
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US8795409B2 (en) | 2011-08-25 | 2014-08-05 | Praxair Technology, Inc. | Air separation plant control |
FR2993363B1 (fr) * | 2012-07-13 | 2015-01-23 | Air Liquide | Procede et dispositif de detection d'un risque de dysfonctionnement dans une unite de separation des composants chimiques d'un produit, notamment de l'air |
WO2015025087A1 (fr) | 2013-08-22 | 2015-02-26 | L'air Liquide,Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Detection de defaillances dans la determination des concentrations de composants chimiques dans une colonne de distillation |
US9708188B1 (en) | 2016-02-22 | 2017-07-18 | Air Products And Chemicals, Inc. | Method for argon production via cold pressure swing adsorption |
US9925514B2 (en) | 2016-02-22 | 2018-03-27 | Air Products And Chemicals, Inc. | Modified chabazite adsorbent compositions, methods of making and using them |
US9669349B1 (en) | 2016-02-22 | 2017-06-06 | Air Products And Chemicals, Inc. | Modified chabazite adsorbent compositions, methods of making and using them |
JP7378695B2 (ja) * | 2020-01-06 | 2023-11-14 | 日本エア・リキード合同会社 | 空気分離システム |
FR3108970B1 (fr) * | 2020-04-02 | 2022-10-28 | Air Liquide | Procédé de démarrage d’une colonne de séparation d’argon d’un appareil de séparation d’air par distillation cryogénique et unité pour mise en œuvre du procédé |
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Publication number | Priority date | Publication date | Assignee | Title |
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US2934908A (en) * | 1954-08-16 | 1960-05-03 | Union Carbide Corp | High argon recovery using proper shelf-top pinch principle |
GB890342A (en) * | 1960-04-25 | 1962-02-28 | Union Carbide Corp | Low temperature air separation with improved argon recovery |
US2934907A (en) * | 1954-08-17 | 1960-05-03 | Union Carbide Corp | High argon recovery using kettle top feed-top pinch principle |
JPS5419165B2 (ko) * | 1973-03-01 | 1979-07-13 | ||
JPS5423073A (en) * | 1977-07-25 | 1979-02-21 | Hitachi Ltd | Method and apparatus for controlling air separating apparatus |
JPS62123279A (ja) * | 1985-11-22 | 1987-06-04 | 株式会社日立製作所 | 空気分離装置の制御方法 |
US4801209A (en) * | 1986-01-17 | 1989-01-31 | The Boc Group, Inc. | Process and apparatus for analyzing a gaseous mixture and a visible emission spectrum generator therefor |
JPS63263381A (ja) * | 1987-04-20 | 1988-10-31 | 住友金属工業株式会社 | 原料アルゴン中の窒素濃度制御法 |
US4784677A (en) * | 1987-07-16 | 1988-11-15 | The Boc Group, Inc. | Process and apparatus for controlling argon column feedstreams |
US4842625A (en) * | 1988-04-29 | 1989-06-27 | Air Products And Chemicals, Inc. | Control method to maximize argon recovery from cryogenic air separation units |
JPH03244990A (ja) * | 1990-02-22 | 1991-10-31 | Sumitomo Metal Ind Ltd | 原料アルゴン中の窒素濃度の制御方法 |
US5313800A (en) * | 1993-02-01 | 1994-05-24 | Praxair Technology, Inc. | Process for maximizing the recovery of argon from an air separation system at high argon recovery rates |
-
1993
- 1993-02-01 US US08/011,605 patent/US5313800A/en not_active Expired - Lifetime
-
1994
- 1994-01-31 EP EP94101420A patent/EP0609814B1/en not_active Expired - Lifetime
- 1994-01-31 JP JP6027455A patent/JPH06241653A/ja not_active Withdrawn
- 1994-01-31 KR KR1019940001673A patent/KR940020083A/ko active IP Right Grant
- 1994-01-31 ES ES94101420T patent/ES2101363T3/es not_active Expired - Lifetime
- 1994-01-31 BR BR9400397A patent/BR9400397A/pt not_active IP Right Cessation
- 1994-01-31 DE DE69402572T patent/DE69402572T2/de not_active Expired - Fee Related
- 1994-01-31 CN CN94101106A patent/CN1092519A/zh active Pending
- 1994-01-31 CA CA002114573A patent/CA2114573A1/en not_active Abandoned
- 1994-05-13 US US08/242,391 patent/US5448893A/en not_active Expired - Lifetime
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BR9400397A (pt) | 1994-08-23 |
EP0609814B1 (en) | 1997-04-16 |
JPH06241653A (ja) | 1994-09-02 |
ES2101363T3 (es) | 1997-07-01 |
DE69402572D1 (de) | 1997-05-22 |
DE69402572T2 (de) | 1997-10-23 |
EP0609814A1 (en) | 1994-08-10 |
CA2114573A1 (en) | 1994-08-02 |
US5448893A (en) | 1995-09-12 |
CN1092519A (zh) | 1994-09-21 |
US5313800A (en) | 1994-05-24 |
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