JP3181546B2 - Method and apparatus for producing nitrogen and argon from air - Google Patents
Method and apparatus for producing nitrogen and argon from airInfo
- Publication number
- JP3181546B2 JP3181546B2 JP34483997A JP34483997A JP3181546B2 JP 3181546 B2 JP3181546 B2 JP 3181546B2 JP 34483997 A JP34483997 A JP 34483997A JP 34483997 A JP34483997 A JP 34483997A JP 3181546 B2 JP3181546 B2 JP 3181546B2
- Authority
- JP
- Japan
- Prior art keywords
- argon
- column
- liquid
- oxygen
- rectification column
- 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 - Fee Related
Links
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
- F25J3/04248—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
- F25J3/04296—Claude expansion, i.e. expanded into the main or 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
- F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
- F25J3/04333—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using quasi-closed loop internal vapor compression refrigeration cycles, e.g. of intermediate or oxygen enriched (waste-)streams
- F25J3/04351—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using quasi-closed loop internal vapor compression refrigeration cycles, e.g. of intermediate or oxygen enriched (waste-)streams of nitrogen
-
- 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
- F25J3/044—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 single pressure main column system only
-
- 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
-
- 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
- F25J3/0466—Producing crude argon in a crude argon column as a parallel working rectification column or auxiliary column system in a single 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
- F25J3/04642—Recovering noble gases from air
- F25J3/04648—Recovering noble gases from air argon
- F25J3/04721—Producing pure argon, e.g. recovered from a crude argon column
- F25J3/04733—Producing pure argon, e.g. recovered from a crude argon column using a hybrid system, e.g. using adsorption, permeation or catalytic reaction
- F25J3/04739—Producing pure argon, e.g. recovered from a crude argon column using a hybrid system, e.g. using adsorption, permeation or catalytic reaction in combination with an auxiliary pure argon 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
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/76—Refluxing the column with condensed overhead gas being cycled in a quasi-closed loop refrigeration cycle
-
- 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
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/82—Processes or apparatus using other separation and/or other processing means using a reactor with combustion or catalytic reaction
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、近時半導体製造工
場で使用分野が拡大しつつある高純度液体アルゴン（純
度99.999 vol％以上）を高純度窒素ガスと同時に空気分
離により製造するための方法および装置、別の言い方を
すれば、深冷分離装置によって原料空気の各成分を精留
分離する際に、単式空気精留塔を用いて圧力下の高純度
窒素ガスおよび高純度液体アルゴンを製造する方法およ
び装置に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing high-purity liquid argon (purity of 99.999 vol% or more), which has recently been used in semiconductor manufacturing plants, by air separation simultaneously with high-purity nitrogen gas. In other words, when rectifying and separating each component of raw air using a cryogenic separation device, high-purity nitrogen gas and high-purity liquid argon are produced under pressure using a single air rectification column. And a method and apparatus for performing the method.
【０００２】[0002]
【従来の技術】〈深冷分離〉 半導体工業においては、空気の深冷分離により得られる
高純度のガスが使われる。この場合、半導体製造工場に
隣接して深冷分離装置を設置し、直接パイピングにより
高純度窒素ガス（日本工業規格の純度99.999 vol％以
上）を供給する方式（オンサイト方式）が普及してい
る。2. Description of the Related Art <Cryogenic separation> In the semiconductor industry, high-purity gas obtained by cryogenic separation of air is used. In this case, a method (on-site method) in which a cryogenic separation device is installed adjacent to a semiconductor manufacturing plant and high-purity nitrogen gas (purity of 99.999 vol% or more according to Japanese Industrial Standards) is supplied by direct piping has become widespread. .
【０００３】〈複式精留塔方式〉 従来、空気からの窒素ガスと液体アルゴンの同時採取
は、主精留塔として上部塔と下部塔とを有する複式精留
塔を使用することによって実施されてきた。この複式精
留塔方式のうちの低圧方式にあっては、比較的高い圧力
（５〜８kg/cm2G)の下部塔の下部に液体空気（Ｏ2 : ３
０〜４０ vol％）、上部に液体窒素を生成させると共
に、比較的低い圧力(0.2〜0.9 kg/cm2G)の上部塔の塔上
部にこの下部塔で採取した液体窒素を還流液として供給
し、同塔中部には液体空気を供給して精留分離すること
により、上部塔内では、塔頂部に窒素ガス、中段部にア
ルゴン濃縮ガス層、塔下部に液体酸素を生成させる。<Compound rectification column method> Conventionally, simultaneous sampling of nitrogen gas and liquid argon from air has been carried out by using a compound rectification column having an upper column and a lower column as a main rectification column. Was. In the low-pressure system of the double rectification column system, liquid air (O 2 : 3) is placed under the lower column at a relatively high pressure (5 to 8 kg / cm 2 G).
0 to 40 vol%), liquid nitrogen is generated in the upper part, and liquid nitrogen collected in the lower tower is supplied as a reflux liquid to the upper part of the upper tower at a relatively low pressure (0.2 to 0.9 kg / cm 2 G). Then, liquid air is supplied to the middle part of the tower to perform rectification and separation, so that nitrogen gas is generated at the top of the tower, an argon-enriched gas layer is formed at the middle part, and liquid oxygen is generated at the bottom of the tower.
【０００４】この複式精留塔方式は、工業的な窒素ガス
（または液体窒素）とアルゴンガス（または液体アルゴ
ン）、さらには酸素ガス（または液体酸素）の製造方法
として広く普及している。The double rectification column system is widely used as an industrial method for producing nitrogen gas (or liquid nitrogen) and argon gas (or liquid argon), and also oxygen gas (or liquid oxygen).
【０００５】複式精留塔において下部塔を不可欠とする
理由は、原料空気を昇圧するための動力は比較的多く必
要とするものの、下部塔で原料空気の全量を液化させる
ことにより得た液体空気および液体窒素が保持している
寒冷エネルギーを、深冷分離装置全体の寒冷源として利
用することに主眼があるからである。[0005] The reason why the lower column is indispensable in the double rectification column is that although the power for pressurizing the raw air is relatively large, the liquid air obtained by liquefying the whole amount of the raw air in the lower column is required. This is because the main purpose is to utilize the cold energy held by liquid nitrogen as a cold source for the entire cryogenic separation device.
【０００６】そして上部塔における窒素ガスとアルゴン
濃縮ガス層並びに液体酸素への精留分離は、各々のガス
固有の沸点差および組成差を要因とする化学工学の法則
に基いた理論段数および実施データをつき合わせること
で解析されている。すなわち、下部塔での液体空気およ
び液体窒素の生成と、上部塔での窒素ガスと液体酸素の
精留分離並びに特にアルゴン濃縮ガス層の生成とが、そ
れぞれの塔ごとに機能分担されている。[0006] The rectification and separation into the nitrogen gas and argon enriched gas layers and liquid oxygen in the upper column is performed by the number of theoretical plates and the actual data based on the law of chemical engineering due to the difference in boiling point and composition difference of each gas. It is analyzed by matching. In other words, the production of liquid air and liquid nitrogen in the lower tower, the rectification and separation of nitrogen gas and liquid oxygen in the upper tower, and particularly the production of an argon-enriched gas layer are shared among the respective columns.
【０００７】〈単式精留塔方式〉 下記の特許出願には、空気から窒素およびアルゴン（さ
らには酸素）を採取するにあたり、単式精留塔を用いる
ことが示されている。 (a) 特公平７−９２３２５号公報（特開昭６１−２８９
２８４号公報） (b) 特公平６−１０４１７５号公報（特開平２−１２２
８０９号公報） (c) 特開平６−２４１６４９号公報<Single Type Rectification Column System> The following patent application discloses that a single type rectification column is used to collect nitrogen and argon (further, oxygen) from air. (a) Japanese Patent Publication No. Hei 7-92325 (JP-A-61-289)
284) (b) JP-B-6-104175 (JP-A-2-122)
809) (c) JP-A-6-241649
【０００８】(a) においては、蒸留帯域において空気を
酸素富化液留分と窒素富化液留分とに分離し、窒素富化
液留分から第１の流れを取り出し、その第１の流れと酸
素富化液の流れとを混合することを含む空気分離方法に
おいて、窒素富化蒸気の第２流を凝縮しそれによって液
体窒素を形成するように、その得られた酸素と窒素との
混合物の少なくとも一部を窒素富化蒸気の第２の流れと
熱交換するようにしている。精留塔頂部の凝縮器の冷却
と精留塔下部の再蒸発器の加熱は、通常の熱ポンプによ
り行っている。精留塔内の圧力は、たとえば 3 ata (2.
1 kg/cm2G)である。アルゴン富化生成物は、補助塔（粗
アルゴン塔）より得られる。補助塔頂部の凝縮器の冷却
と補助塔下部の再蒸発器の加熱も、通常の熱ポンプによ
り行っている。In (a), in a distillation zone, air is separated into an oxygen-enriched liquid fraction and a nitrogen-enriched liquid fraction, and a first stream is taken out of the nitrogen-enriched liquid fraction, Separation process comprising mixing a stream of oxygen-enriched liquid with a stream of oxygen-enriched liquid, the resulting mixture of oxygen and nitrogen to condense a second stream of nitrogen-enriched vapor and thereby form liquid nitrogen. Is exchanged with the second stream of nitrogen-enriched steam. Cooling of the condenser at the top of the rectification column and heating of the re-evaporator at the bottom of the rectification column are performed by a normal heat pump. The pressure in the rectification column is, for example, 3 ata (2.
1 kg / cm 2 G). The argon-enriched product is obtained from an auxiliary column (crude argon column). The cooling of the condenser at the top of the auxiliary tower and the heating of the re-evaporator at the bottom of the auxiliary tower are also performed by ordinary heat pumps.
【０００９】(b) においては、空気からアルゴンと窒素
を製造するにあたり、ＰＳＡユニットやメンブラン分離
ユニットを用いて窒素とアルゴンが濃縮された生成物
（少量の酸素を含む）の流れを生じさせ、これをその露
点近くまで冷却してから精留塔に導入して、オーバーヘ
ッド窒素フラクションおよび酸素のほとんどを含有した
ボトムフラクションを形成させる。系の冷源には、主と
して窒素ガスを用いるか、あるいは外部からのアルゴン
／窒素混合物または酸素／窒素混合物を用いる。精留塔
から取り出した側留はＰＳＡユニットで分離され、粗ア
ルゴン、生成物、窒素、廃棄物流れを生じる。精留塔の
圧力は、たとえば 45 psia (2.13 kg/cm2G）程度であ
る。製品は、液体粗アルゴンと窒素ガスである。In (b), in producing argon and nitrogen from air, a stream of a product (including a small amount of oxygen) in which nitrogen and argon are concentrated is generated using a PSA unit or a membrane separation unit, This is cooled to near its dew point and then introduced into the rectification column to form an overhead nitrogen fraction and a bottoms fraction containing most of the oxygen. As the cold source of the system, nitrogen gas is mainly used, or an external argon / nitrogen mixture or oxygen / nitrogen mixture is used. The side stream removed from the rectification column is separated in a PSA unit to produce crude argon, product, nitrogen and waste streams. The pressure in the rectification column is, for example, about 45 psia (2.13 kg / cm 2 G). The products are liquid crude argon and nitrogen gas.
【００１０】(c) においては、単式精留塔を用いて、圧
力下のガス状酸素、圧力下のガス状窒素、液体酸素、液
体窒素およびアルゴンを得ている。精留塔内の圧力分布
は、1.3 〜 2 bar (0.3 〜 1 kg/cm2G) である。この
(c) は窒素冷凍回路にかかるものであり、言わば空気か
ら全成分を分離するベーシックな方法ということができ
る。In (c), gaseous oxygen under pressure, gaseous nitrogen under pressure, liquid oxygen, liquid nitrogen and argon are obtained using a single type rectification column. The pressure distribution in the rectification column is 1.3 to 2 bar (0.3 to 1 kg / cm 2 G). this
(c) relates to a nitrogen refrigeration circuit, which can be said to be a basic method of separating all components from air.
【００１１】〈単式精留塔による酸素の採取〉 単式精留塔に関して付言するに、従来より製品としての
酸素ガス採取専用の深冷分離装置が使用されているが、
ここで使用されている単式精留塔は、空気成分のうち最
も沸点が高いために液化・精留しやすい酸素ガスのみの
取得を目的としているため、塔下部に液体空気を溜める
方式（複式精留塔の下部塔に類似している）を採用して
いる。ただしこの方式は、精留のための理論段数が低い
ので窒素ガスの純度が悪く、日本工業規格を満たす高純
度窒素ガスの製造方法としては使用できない。また液体
アルゴンを採取するために不可欠な条件であるアルゴン
濃縮ガス層が形成されていないため、高純度窒素ガスと
高純度液体アルゴンとを同時に製造することはできな
い。<Sampling of Oxygen by Single-Type Rectification Column> In addition to the single-type rectification column, a cryogenic separation device dedicated to collecting oxygen gas as a product has been conventionally used.
The single-column rectification column used here aims to obtain only oxygen gas that has the highest boiling point among the air components and is easily liquefied and rectified. (Similar to the lower tower of the retaining tower). However, this method has a low number of theoretical plates for rectification, so the purity of nitrogen gas is poor, and cannot be used as a method for producing high-purity nitrogen gas that meets Japanese Industrial Standards. Since an argon-enriched gas layer, which is an essential condition for collecting liquid argon, is not formed, high-purity nitrogen gas and high-purity liquid argon cannot be produced at the same time.
【００１２】[0012]
【発明が解決しようとする課題】〈複式精留塔方式〉 上に述べた複式精留塔による空気の分離方式は、半導体
製造工場向けには採取不要であることが多い液体酸素を
生成させるため、その液体酸素の持つ寒冷エネルギーを
有効利用していないこと、精留塔が複雑となり、装置コ
ストも高くなることなどの問題点がある。すなわち、こ
の方式は空気から窒素、酸素、アルゴンの全てを採取す
るような目的には適していると言うことができるが、高
純度窒素ガスと高純度液体アルゴンとを同時に製造する
技術にかかる本発明とは目的が相違している。[Problem to be Solved by the Invention] Double rectification tower system The above-mentioned double rectification column air separation system generates liquid oxygen which is often unnecessary for a semiconductor manufacturing plant. However, there is a problem that the refrigeration energy of the liquid oxygen is not effectively used, the rectification column is complicated, and the equipment cost is high. In other words, it can be said that this method is suitable for the purpose of collecting all of nitrogen, oxygen, and argon from air, but this method is related to the technology for simultaneously producing high-purity nitrogen gas and high-purity liquid argon. The purpose is different from the invention.
【００１３】〈単式精留塔方式〉 上に述べた３つの出願(a), (b), (c) に開示の単式精留
塔方式においては、取得しようとする製品やその純度、
冷源、経済性などを考慮して、それぞれの目的に応じた
装置上や操作上の工夫を行っているが、冷源として液体
酸素を用い、製品として高純度窒素ガスと高純度液体ア
ルゴンとを同時に採取し、隣接する半導体製造工場にそ
れらの製品を供給するという機構や目的には適していな
い。<Single Type Rectification Column System> In the single type rectification column system disclosed in the above three applications (a), (b) and (c), the product to be obtained, its purity,
Considering the cold source, economics, etc., we have devised the equipment and operation according to each purpose, but use liquid oxygen as a cold source and use high-purity nitrogen gas and high-purity liquid argon as products. Is not suitable for the mechanism and purpose of simultaneously sampling and supplying those products to an adjacent semiconductor manufacturing plant.
【００１４】〈本発明の目的〉 本発明は、このような背景下において、空気の分離を単
式精留塔を用いて行うと共に、低圧力下での精留、製品
窒素ガスの一部を再液化した還流液の利用、製品として
は採取不要な液体酸素の保持する寒冷エネルギーの利用
などを配慮することにより、液体アルゴンの高収率取
得、電力原単位の低減、立上げ時間の短縮、各機器の単
純化と装置製作コストの低減を図ることのできる、高純
度窒素ガスおよび高純度液体アルゴンの工業的に有利な
製造方法および装置を提供することを目的とするもので
ある。<Object of the present invention> Under such a background, the present invention performs air separation using a single type of rectification column, rectifies under low pressure, and recycles a part of product nitrogen gas. By considering the use of liquefied reflux liquid and the use of cold energy that holds liquid oxygen that does not need to be collected as a product, it is possible to obtain a high yield of liquid argon, reduce the power consumption unit, shorten the startup time, It is an object of the present invention to provide an industrially advantageous method and apparatus for producing high-purity nitrogen gas and high-purity liquid argon, which can simplify the equipment and reduce the production cost of the apparatus.
【００１５】[0015]
【課題を解決するための手段】本発明の空気からの窒素
およびアルゴンの製造方法は、原料空気を精留塔にて精
留することにより、製品として、高純度窒素ガスおよび
高純度液体アルゴンを得る方法であって、精留塔とし
て単式精留塔(10)を用いること、’単式精留塔(10)に
おける精留を、 0.1〜 0.5 kg/cm 2 Gの低圧条件下に行う
こと、単式精留塔(10)の下部に生成する液体酸素につ
いては、その全部または大部分を系の主たる冷源として
使用すること、’このとき、単式精留塔(10)の下部に
溜まる液体酸素を、その一部については、液化・過冷却
器(9) の冷媒として使用して液体酸素が保有している寒
冷エネルギーを利用した後に、単式精留塔(10)中段のア
ルゴン濃縮層上部に返送し、他部については、液化・過
冷却器(9) の冷媒として使用した後、主熱交換器(8) に
導入して原料空気の冷媒として使用してから、最終的に
冷熱を喪失して気化した廃酸素ガスとして大気に放出す
ること、単式精留塔(10)の頂部に生成する高純度窒素
ガスについては、その大部分を冷源として使用した後に
製品としての高純度窒素ガスとして取り出すこと、単
式精留塔(10)の中間部に生成するアルゴン濃縮ガス層に
ついては、それを粗アルゴン塔(12)を経てアルゴン精製
装置(22)、さらには精製アルゴン塔(23)に導き、製品と
しての高純度液体アルゴンを得ること、および、 ’粗
アルゴン塔(12)下部にリボイラー(12a) を設けると共
に、そのリボイラー(12a) 管外に貯留される凝縮液を制
御するために、粗アルゴン塔(12)の底部から単式精留塔
(10)への流路に設けた液面調節弁(21)を、粗アルゴン塔
(12)下部に設けた液面指示計(20)により制御するように
したこと、を特徴とするものである。According to the method of the present invention for producing nitrogen and argon from air, high-purity nitrogen gas and high-purity liquid argon are produced as products by rectifying raw air in a rectification column. Using a single rectification column (10) as the rectification column,
Rectification under low pressure conditions of 0.1 to 0.5 kg / cm 2 G
It, for the liquid oxygen to produce the bottom of the simplex fractionator (10), use that all or most of the primary cooling source of the system, 'this time, the bottom of the simplex fractionator (10)
Liquid oxygen that accumulates, part of it is liquefied and supercooled
Used as a refrigerant for the vessel (9)
After using cold energy, the middle stage of the single-stage rectification tower (10)
Return to the upper part of the Lugon enrichment layer, and liquefy and
After using it as a refrigerant for the cooler (9), it is transferred to the main heat exchanger (8).
After being introduced and used as a refrigerant for the raw material air,
Released to the atmosphere as waste oxygen gas vaporized due to loss of cold heat
That, for high-purity nitrogen gas generated at the top of the single-column rectification tower (10), after using most of it as a cold source, take out as high-purity nitrogen gas as a product , the single-column rectification tower (10) The argon-enriched gas layer generated in the middle part of the above is led through a crude argon column (12) to an argon purifier (22) and further to a purified argon column (23) to obtain high-purity liquid argon as a product That and the 'coarse
When a reboiler (12a) is installed below the argon tower (12),
Control the condensate stored outside the reboiler (12a).
In order to control, a simple rectification column was set up from the bottom of the crude argon column (12).
The liquid level control valve (21) provided in the flow path to (10) is
(12) As controlled by the liquid level indicator (20) provided at the bottom
It is characterized by having done .
【００１６】本発明の空気からの窒素およびアルゴンの
製造装置は、原料空気を精留塔にて精留することによ
り、製品として、高純度窒素ガスおよび高純度液体アル
ゴンを得るための装置であって、精留塔が単式精留塔
(10)であること、単式精留塔(10)の下部に生成する液
体酸素の全部または大部分を、主熱交換器(8) および液
化・過冷却器(9) を含む系の主たる冷源として使用する
ための管路を備えていること、’このとき、単式精留
塔(10)の下部に溜まる液体酸素を、その一部について
は、液化・過冷却器(9) の冷媒として使用して液体酸素
が保有している寒冷エネルギーを利用した後に、単式精
留塔(10)中段のアルゴン濃縮層上部に返送し、他部につ
いては、液化・過冷却器(9) の冷媒として使用した後、
主熱交換器(8) に導入して原料空気の冷媒として使用し
てから、最終的に冷熱を喪失して気化した 廃酸素ガスと
して大気に放出するための管路をそれぞれ備えているこ
と、単式精留塔(10)の頂部に生成する高純度窒素ガス
の大部分を系内の冷源として使用した後に製品としての
高純度窒素ガスとして取り出すための管路を備えている
こと、単式精留塔(10)の中間部に生成するアルゴン濃
縮ガス層を蒸留して粗アルゴンを得るための粗アルゴン
塔(12)と、粗アルゴン中の酸素を除去するためのアルゴ
ン精製装置(22)と、酸素が除去された変成アルゴンを精
留して高純度液体アルゴンを得るための精製アルゴン塔
(23)とを備えていること、および、 ’粗アルゴン塔(1
2)下部にリボイラー(12a) を設けると共に、そのリボイ
ラー(12a) 管外に貯留される凝縮液を制御するために、
粗アルゴン塔(12)の底部から単式精留塔(10)への流路に
液面調節弁(21)を設け、かつその液面調節弁(21)を制御
するめの液面指示計(20)を粗アルゴン塔(12)下部に設け
たこと、を特徴とするものである。The apparatus for producing nitrogen and argon from air of the present invention is an apparatus for obtaining high-purity nitrogen gas and high-purity liquid argon as products by rectifying raw air in a rectification tower. The rectification tower is a simple rectification tower
(10), and all or most of the liquid oxygen generated at the bottom of the single-column rectification column (10) is transferred to the main cooling system of the system including the main heat exchanger (8) and the liquefaction / supercooler (9). that it comprises a conduit for use as a source, 'this time, single direction rectification
Liquid oxygen collected at the bottom of the tower (10)
Is the liquid oxygen used as a refrigerant in the liquefaction / supercooler (9).
After using the cold energy held by
Return to the upper part of the argon concentration layer in the middle stage of the distillation tower (10), and
After use as a refrigerant in the liquefaction / supercooler (9),
It is introduced into the main heat exchanger (8) and used as a refrigerant for raw air.
After that, the waste oxygen gas which was finally
And have pipes for release to the atmosphere.
And a line for taking out most of the high-purity nitrogen gas generated at the top of the single-column rectification column (10) as a high-purity nitrogen gas as a product after using it as a cold source in the system
That is, a crude argon column (12) for obtaining crude argon by distilling an argon-enriched gas layer generated in the middle part of the single-column rectification column (10), and an argon purifying device for removing oxygen in the crude argon (22) and a purified argon column for rectifying denatured argon from which oxygen has been removed to obtain high-purity liquid argon
(23) and the 'crude argon column (1
2) Install a reboiler (12a) at the bottom and
(12a) To control the condensate stored outside the pipe,
In the flow path from the bottom of the crude argon column (12) to the simple distillation column (10)
Provide level control valve (21) and control the level control valve (21)
A liquid level indicator (20) is provided below the crude argon column (12).
It is characterized by that.
【００１７】[0017]
【発明の実施の形態】以下本発明を詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
【００１８】〈フローシート〉 本発明は上記の、、およびを特徴的かつ必須の
構成要件とするものである。本発明は、より具体的に
は、図１にフローシートを示した以下の一連の工程によ
り実施される。この図１は典型的なケースを示したもの
であり、各成分の流路やＪ−Ｔ弁(JT)の設置態様には、
これ以外にも当業者にとっては容易に設計可能ないくつ
かのバリエーションが可能である。<Flow Sheet> The present invention is characterized by the above and the above as characteristic and indispensable components. More specifically, the present invention is carried out by the following series of steps, the flow sheet of which is shown in FIG. FIG. 1 shows a typical case, and the flow path of each component and the installation mode of a JT valve (JT) include:
In addition, several variations that can be easily designed by those skilled in the art are possible.
【００１９】（１）原料空気を吸入塔(1) を経てフィル
タ(2) で除塵した後、空気圧縮機(3)で５〜１０kg/cm2G
に圧縮する。(1) After removing the dust from the raw air through a suction tower (1) and a filter (2), the air is compressed by an air compressor (3) to 5 to 10 kg / cm 2 G.
Compress to
【００２０】（２）除塵、圧縮した原料空気を、原料空
気に微量含まれているＣＯおよびＨ2を空気中の酸素で
ＣＯ2 およびＨ2 Ｏに酸化するための貴金属酸化触媒が
充填されかつ１００〜２００℃に加温した触媒塔(4) に
導入する。(2) A noble metal oxidation catalyst for oxidizing the dust-removed and compressed raw air into CO 2 and H 2 O with CO in the raw air and H 2 contained in a trace amount by oxygen in the air is filled in; It is introduced into the catalyst tower (4) heated to 100 to 200 ° C.
【００２１】（３）触媒塔(4) から導出された原料空気
を、次工程のために大気温度付近まで空気を冷却する水
洗冷却塔(5) あるいは図示せざる熱交換器式冷却塔に導
入する。(3) The raw material air derived from the catalyst tower (4) is introduced into a washing cooling tower (5) for cooling the air to near the atmospheric temperature or a heat exchanger type cooling tower (not shown) for the next step. I do.
【００２２】（４）そこから導出された原料空気を、原
料空気に微量含まれていてかつ上記（２）の工程で生成
するＣＯ2 とＨ2 Ｏを大気温度付近で吸着するために、
ゼオライト等の吸着剤を充填した圧力変動再生式等の常
温の吸着塔(7) に導入する。(4) In order to adsorb CO 2 and H 2 O generated in the above step (2) in a small amount in the raw material air derived therefrom and adsorbing CO 2 and H 2 O near the atmospheric temperature,
It is introduced into a normal temperature adsorption tower (7), such as a pressure fluctuation regeneration type, filled with an adsorbent such as zeolite.
【００２３】（５）吸着塔(7) から導出された原料空気
を、後述の（８）の単式精留塔(10)より導出される沸点
（−１９６℃）に近い温度の窒素ガス（製品窒素ガスお
よび排窒素ガス）と沸点（−１８３℃）に近い酸素ガス
（排酸素ガス）との冷熱を原料空気と循環窒素に与えて
冷却する主熱交換器(8) に導入する。(5) The raw material air derived from the adsorption tower (7) is converted into nitrogen gas (product) having a temperature close to the boiling point (−196 ° C.) derived from the single-type rectification column (10) of (8) described later. Cooling heat of nitrogen gas and exhaust gas (nitrogen gas) and oxygen gas (exhaust oxygen gas) having a boiling point (-183 ° C.) is supplied to the raw air and circulating nitrogen to be introduced into a main heat exchanger (8) for cooling.
【００２４】（６）このとき、主熱交換器(8) で冷却途
中の原料空気は、その一部を分岐し、断熱膨張により寒
冷を発生させて深冷装置の熱損失の補償とバックアップ
用液体窒素の冷源を得るための膨張タービン(13)に導入
して断熱膨張させてさらに冷却し、膨張タービン(13)を
出た原料空気を液化・過冷却器(9) を通すことにより液
体空気を生成させ、さらにはＪ−Ｔ（ジュール・トムソ
ン膨張）弁(JT)を経て低温にし、後述の単式精留塔(10)
の中部に送入する（または液化・過冷却器(9) を通さず
に直接単式精留塔(10)に送入する）。このとき単式精留
塔(10)への原料空気の導入部は、単式精留塔(10)内部に
生成するアルゴン濃縮ガス層の上側とし、アルゴン濃縮
層を撹乱しないようにすることが重要である。(6) At this time, the raw material air being cooled in the main heat exchanger (8) is partly branched, and cold is generated by adiabatic expansion to compensate for heat loss of the refrigeration system and to provide backup. It is introduced into an expansion turbine (13) for obtaining a cold source of liquid nitrogen, adiabatically expanded and further cooled, and the raw material air exiting the expansion turbine (13) is passed through a liquefaction / supercooler (9) to form a liquid. Air is generated, and the temperature is lowered through a JT (Jule-Thomson expansion) valve (JT).
(Or directly into the single rectification column (10) without passing through the liquefaction / supercooler (9)). At this time, it is important that the introduction part of the raw material air to the single-column rectification column (10) is above the argon-enriched gas layer generated inside the single-column rectification column (10) so as not to disturb the argon-enriched layer. is there.
【００２５】（７）一方、主熱交換器(8) の全域で冷却
された原料空気を、単式精留塔(10)下部の内部に設けた
コンデンサー／リボイラー(11)に導入して（または液化
・過冷却器(9) に送入後）、単式精留塔(10)下部に溜ま
っている周囲の液体酸素およびアルゴンを気化させるた
めの加熱源として使用する。(7) On the other hand, the raw material air cooled in the entire area of the main heat exchanger (8) is introduced into a condenser / reboiler (11) provided inside the lower part of the single-column rectification column (10) (or It is used as a heating source to vaporize the surrounding liquid oxygen and argon stored in the lower part of the single rectification tower (10) after being sent to the liquefaction / supercooler (9).
【００２６】（８）コンデンサー／リボイラー(11)を経
て液化された液体空気（厳密には、気体と液体の二相流
となっている）は、その一部をＪ−Ｔ弁(JT)を経て単式
精留塔(10)中部に導入され、他部をＪ−Ｔ弁(JT)を経て
後述の粗アルゴン塔(12)上部および精製アルゴン塔(23)
上部のコンデンサーの冷媒に使用すると共に、Ｊ−Ｔ弁
(JT)を経て、単式精留塔(10)中段のアルゴン濃縮層上部
に返送する。(8) Liquid air liquefied through the condenser / reboiler (11) (strictly, a two-phase flow of gas and liquid) is partially supplied to the JT valve (JT). Through the JT valve (JT), the other part through a JT valve (JT), the upper part of a crude argon column (12) and a purified argon column (23)
Used for refrigerant in the upper condenser, and J-T valve
After (JT), it is returned to the upper part of the argon concentration layer in the middle stage of the single-column rectification column (10).
【００２７】（９）単式精留塔(10)内では、窒素（大気
圧下の沸点−１９６℃）、アルゴン（大気圧下の沸点−
１８６℃）、酸素（大気圧下の沸点−１８３℃）の沸点
差により、頂部に高純度窒素ガス、中間部にアルゴン濃
縮ガス層、下部に液体酸素が生成される。単式精留塔(1
0)下部には液体酸素液面を保持するための液面調節弁(1
7)を設け、これを液面指示計(16)により制御するように
する。単式精留塔(10)内の圧力は、 0.1〜 0.5 kg/cm
2G、好ましくは 0.2〜 0.3 kg/cm2Gの低圧に保持され
る。高純度窒素ガスは塔頂部より製品高純度窒素ガスと
して抜き出し、アルゴン濃縮ガス層は後述の粗アルゴン
塔(12)に導入する。液体酸素は、次に述べるように主熱
交換器(8) 等の冷媒として活用する。(9) In the single-column rectification column (10), nitrogen (boiling point at atmospheric pressure -196 ° C), argon (boiling point at atmospheric pressure-
186 ° C.) and oxygen (boiling point at atmospheric pressure -183 ° C.) produce a high-purity nitrogen gas at the top, an argon-enriched gas layer at the middle, and liquid oxygen at the bottom. Single rectification tower (1
0) The liquid level control valve (1
7) is provided, and this is controlled by the liquid level indicator (16). The pressure inside the single-column rectification tower (10) is 0.1 to 0.5 kg / cm
It is kept at a low pressure of 2 G, preferably 0.2-0.3 kg / cm 2 G. The high-purity nitrogen gas is extracted from the top of the tower as a product high-purity nitrogen gas, and the argon-enriched gas layer is introduced into a crude argon tower (12) described later. Liquid oxygen is used as a refrigerant for the main heat exchanger (8) as described below.
【００２８】（１０）ここで単式精留塔(10)の下部に溜
まる液体酸素は、その一部については、液化・過冷却器
(9) の冷媒として使用して液体酸素が保有している寒冷
エネルギーを利用した後に、単式精留塔(10)中段のアル
ゴン濃縮層上部に返送する。他部については、液化・過
冷却器(9) の冷媒として使用した後、主熱交換器(8) に
導入して原料空気の冷媒として使用してから、最終的に
冷熱を喪失して気化した廃酸素ガスとして大気に放出す
る。なお、単式精留塔(10)下部に溜まる液体酸素は精留
されていて日本工業規格以上の純度（99.5 vol％）を保
有しているので、必要とする場合には、寒冷源として使
用している残りの一部を製品液体酸素として採取するこ
ともできる。また主熱交換器(8) 等で冷熱エネルギーを
喪失して大気温度近くとなった排酸素ガスも、大気放出
せずに別途圧縮機で昇圧することによって製品酸素ガス
として使用することができる。(10) The liquid oxygen collected in the lower part of the single-column rectification column (10) is partially liquefied and supercooled.
After using the cryogenic energy of liquid oxygen by using it as the refrigerant of (9), it is returned to the upper part of the argon enrichment layer in the middle stage of the single type rectification column (10). The other part is used as a refrigerant for the liquefaction / supercooler (9), then introduced into the main heat exchanger (8) and used as a refrigerant for the raw material air. Released into the atmosphere as waste oxygen gas. The liquid oxygen collected at the bottom of the single-column rectification tower (10) is rectified and has a purity (99.5 vol%) higher than the Japanese Industrial Standards. If necessary, use it as a cold source. The remaining part can be collected as product liquid oxygen. Also, the exhausted oxygen gas which has lost its cooling energy in the main heat exchanger (8) or the like and has become close to the atmospheric temperature can be used as product oxygen gas by separately pressurizing the compressor without releasing it to the atmosphere.
【００２９】（１１）高純度窒素ガスは製品高純度窒素
ガスとしてパイピングにより隣接する半導体製造工場に
送られるが、単式精留塔(10)上部より抜き出す窒素ガス
は、液化・過冷却器(9) を経て主熱交換器(8) にも送ら
れ、さらには吸着塔(7) の再生ガスや蒸発冷却塔(6) の
循環水の蒸発を促進して蒸発潜熱を発生させるガスとし
ても使われ、最終的には廃ガスとして大気に放出され
る。(11) The high-purity nitrogen gas is sent as a product high-purity nitrogen gas to an adjacent semiconductor manufacturing plant by piping. The nitrogen gas extracted from the upper part of the single-column rectification tower (10) is supplied to a liquefaction / supercooler (9). ) To the main heat exchanger (8), and is also used as a regeneration gas in the adsorption tower (7) and a gas that promotes evaporation of circulating water in the evaporative cooling tower (6) to generate latent heat of evaporation. It is eventually released to the atmosphere as waste gas.
【００３０】（１２）一方、粗アルゴン塔(12)に導入さ
れたアルゴン濃縮ガス（アルゴン１０〜１３ vol％）
は、粗アルゴン塔(12)上部のコンデンサーによって冷却
され、沸点の高い酸素ガスは液化されて塔底部から単式
精留塔(10)に戻され、液化されないガスは次に述べるよ
うに粗アルゴンガスとして塔上部から抜き出される。(12) On the other hand, an argon-enriched gas (10 to 13 vol% of argon) introduced into the crude argon column (12)
Is cooled by the condenser at the top of the crude argon column (12), the oxygen gas having a high boiling point is liquefied and returned to the single rectification column (10) from the bottom of the column, and the non-liquefied gas is converted to crude argon gas as described below. It is extracted from the top of the tower.
【００３１】（１３）粗アルゴン塔(12)下部にはリボイ
ラー(12a) を設け、そのリボイラー(12a) 管外に貯留さ
れる凝縮液を制御するために、粗アルゴン塔(12)の底部
から単式精留塔(10)への流路に設けた液面調節弁(21)
を、粗アルゴン塔(12)下部に設けた液面指示計(20)によ
り制御する。このようにすると、粗アルゴン塔(12)下部
に溜まる液体酸素中に残存するアルゴンを再沸させるこ
とにより、アルゴン回収率を高めることができる上、装
置停止時に液面調節弁(21)を全閉にして同塔内の液面を
保持しておくことにより塔内の精留条件が早期に整い、
再起動時の立上げ時間（正常運転復帰時間）を短縮する
ことができる。(13) A reboiler (12a) is provided below the crude argon column (12). In order to control the condensate stored outside the tube of the reboiler (12a), the bottom of the crude argon column (12) is used. Liquid level control valve (21) provided in the flow path to the single type rectification tower (10)
Is controlled by a liquid level indicator (20) provided below the crude argon column (12). By doing so, the argon remaining in the liquid oxygen stored in the lower part of the crude argon column (12) can be reboiled to increase the argon recovery rate, and the liquid level control valve (21) can be completely shut down when the apparatus is stopped. By closing and maintaining the liquid level in the column, the rectification conditions in the column are prepared early,
The start-up time (return time to normal operation) at the time of restart can be shortened.
【００３２】（１４）粗アルゴン塔(12)上部より抜き出
された粗アルゴンガスは、その中に含まれる酸素成分
（ 0.5〜４ vol％）を外部より添加したＨ2 による還元
反応によりＨ2 Ｏに転化して除去するために、貴金属触
媒とゼオライト等の吸着剤を充填したアルゴン精製装置
(22)に導入される。[0032] (14) the crude argon column (12) crude argon gas withdrawn from the top, H 2 by reduction with H 2 added oxygen component contained therein to (0.5 to 4 vol%) from the outside An argon purifier filled with a noble metal catalyst and an adsorbent such as zeolite to remove it by converting it to O
(22) is introduced.
【００３３】（１５）酸素を除去された、窒素ガス、ア
ルゴンガス並びに過剰に添加されている水素ガスの３成
分混合ガスとなった変成アルゴンガスは、これを低温精
留によって分離するために、精製アルゴン塔(23)に導入
される。精製アルゴン塔(23)上部コンデンサー内の冷媒
の液体空気により、沸点の高いアルゴンは液化して塔下
部に向けて流下し、塔底部から製品高純度液体アルゴン
として採取される。そして高純度液体アルゴンを貯蔵す
るために、図示せざる製品液体アルゴンタンク（コール
ドエバポレーター）を設置する。液化しない窒素ガスや
過剰に添加された水素ガスは、精製アルゴン塔(23)の頂
部より放出され、熱交換後大気に廃棄される。なお、粗
アルゴン塔(12)で粗アルゴンを得た後のアルゴン精製工
程としてＰＳＡ方式を採用することもできるが、別途液
化工程を併設しない場合は高純度液体アルゴンとして貯
蔵しておくことができなくなる。(15) The modified argon gas, which has become a ternary mixed gas of nitrogen gas, argon gas and excessively added hydrogen gas from which oxygen has been removed, is separated by low-temperature rectification. The purified argon column (23) is introduced. The high-boiling argon is liquefied by the liquid air of the refrigerant in the upper condenser of the purified argon tower (23), liquefied and flows down toward the lower part of the tower, and is collected as high-purity liquid argon from the bottom of the tower. Then, a product liquid argon tank (cold evaporator) (not shown) is installed to store high-purity liquid argon. Non-liquefied nitrogen gas and excessively added hydrogen gas are discharged from the top of the refined argon column (23), and are discarded to the atmosphere after heat exchange. The PSA method can be used as an argon purification step after obtaining crude argon in the crude argon column (12), but if no separate liquefaction step is provided, it can be stored as high-purity liquid argon. Disappears.
【００３４】（１６）付属設備として、製品高純度窒素
ガスの使用量の変動あるいは停電時に備えるために、単
式精留塔(10)上部受液槽に少量併産した高純度液体窒素
を送入するための、バックアップ用液体窒素タンク（コ
ールドエバポレーター）(18)を設備する。この液体窒素
は、本発明の空気分離装置を再起動する際の立ち上げ時
間を短縮するための外部寒冷源として、単式精留塔(10)
上部に還流させることにより有効に活用することができ
る。なおこの液体窒素は、製品窒素ガスの減量運転が可
能なときに製造することが可能である。(16) As a supplementary equipment, a small amount of high-purity liquid nitrogen co-produced in the upper part of the single rectification tower (10) is sent in order to prepare for fluctuations in the amount of high-purity nitrogen gas used or in the event of a power outage. A backup liquid nitrogen tank (cold evaporator) (18) is installed to perform the operation. This liquid nitrogen is used as a single rectification column (10) as an external refrigeration source for shortening the startup time when restarting the air separation device of the present invention.
It can be effectively used by refluxing to the upper part. Note that this liquid nitrogen can be produced when the product nitrogen gas can be reduced in operation.
【００３５】こうすることによって、本発明において
は、液体空気を周囲の液体酸素を沸騰させるリボイラー
(11)の加熱源として活用することができ、製品として使
用しない液体酸素の冷熱エネルギーを最大限利用するこ
とができ、また原料空気中に含有されているアルゴンの
損失を少なくすること（液体空気の大気放出をしないこ
と）によって、単式精留塔による高純度窒素ガスと高純
度液体アルゴンとの同時採取を可能にしている。By doing so, in the present invention, a reboiler for boiling liquid air into surrounding liquid oxygen is provided.
(11) It can be used as a heating source, can make maximum use of the cooling energy of liquid oxygen not used as a product, and reduces the loss of argon contained in the raw air (liquid air Of the high purity nitrogen gas and the high purity liquid argon by the single type rectification column at the same time.
【００３６】〈公知の単式精留塔との対比〉 本発明においては、上記(a), (b), (c）とは異なり、製
品としては採取不要であることが多い液体酸素（採取対
象であるアルゴンは原料空気対比で0.03 vol％程度まで
に低下されている）が保持する寒冷エネルギーを主たる
冷源として有効に活用している。<Comparison with known single-column rectification column> In the present invention, unlike the above (a), (b), and (c), liquid oxygen (collection target) is often unnecessary as a product. (Argon is reduced to about 0.03 vol% compared to the raw material air.)) The cold energy that is maintained is effectively used as the main cold source.
【００３７】また公知の単式精留塔方式においては液体
空気を主熱交換器等の寒冷源に使用した後に大気放出し
ているが、本発明においては液体空気（アルゴンは、原
料空気中の含有量である 0.9 vol％）の全量を精留塔に
おいて精留分離操作しているので、製品としての液体ア
ルゴンの取得量が最大となる。より詳しく述べると、窒
素ガスの採取を目的としている公知の単式精留方式にお
いては、膨張タービンに送入する寒冷発生用ガスとして
原料空気（ 0.9 vol％）中よりもアルゴンが濃縮（ 1.5
〜３ vol％）されている液体空気の気化ガスを使用する
ために、主熱交換器を経て大気温度近くに戻り、アルゴ
ンを含有したまま大気へ放出されているが、本発明にお
いては、寒冷発生用ガスとして主熱交換器(8) での冷却
途中の原料空気の一部を分岐して膨張タービン(13)へ送
入し、断熱膨張により冷却した後に、液化・過冷却器
(9) へ導入して過冷却液体空気として単式精留塔(10)中
部へ送入しているために、主熱交換器(8) 全域を通過す
るもう一方の原料空気と合わせての原料空気全量を精留
・分離するために、原料空気中に含まれている全てのア
ルゴンが精留の対象となり、目的物であるアルゴンの収
量を最大にすることができる。In the known single-column rectification column system, liquid air is discharged to the atmosphere after being used as a cold source such as a main heat exchanger. In the present invention, liquid air (argon is contained in the raw material air) is used. (0.9 vol%) is rectified and separated in the rectification column, so that the amount of liquid argon obtained as a product is maximized. More specifically, in a known single-column rectification system for the purpose of collecting nitrogen gas, argon is concentrated (1.5 vol.%) From the raw air (0.9 vol%) as a cold generation gas fed to the expansion turbine.
In order to use the vaporized gas of liquid air which has been discharged to the atmosphere temperature through the main heat exchanger, it is released to the atmosphere while containing argon. A part of the raw material air in the course of cooling in the main heat exchanger (8) is branched off as the generating gas, sent to the expansion turbine (13), and cooled by adiabatic expansion.
The raw material combined with the other raw material air passing through the entire main heat exchanger (8) because it is introduced into (9) and sent as supercooled liquid air to the central part of the single-column rectification column (10) In order to rectify and separate the whole amount of air, all argon contained in the raw material air is subjected to rectification, and the yield of the target product, argon, can be maximized.
【００３８】[0038]
【実施例】次に実施例をあげて本発明をさらに説明す
る。The present invention will be further described with reference to the following examples.
【００３９】実施例１ 図１は、本発明に基く高純度窒素ガスおよび高純度液体
アルゴンの製造工程の一例を示したフローシートであ
る。図中、一点鎖線で囲んだ部分はコールドボックス(1
5)である。Example 1 FIG. 1 is a flow sheet showing an example of a process for producing high-purity nitrogen gas and high-purity liquid argon based on the present invention. In the figure, the part surrounded by the dashed line is the cold box (1
5).
【００４０】原料空気は、流路Ａに沿って吸入塔(1) よ
り導入され、フィルター(2) で除塵された後、空気圧縮
機(3) で８〜１０kg/cm2G に加圧される。The raw material air is introduced from the suction tower (1) along the flow path A, and after dust is removed by the filter (2), it is pressurized to 8 to 10 kg / cm 2 G by the air compressor (3). You.
【００４１】ついで、触媒塔(4) にて、上記原料空気中
のＣＯおよびＨ2 を空気中の酸素でＣＯ2 およびＨ2 Ｏ
に酸化する貴金属酸化触媒体と高温で接触させ、次工程
のために大気温度付近まで空気を冷却する水洗冷却塔
(5) に導入され、冷却される。Then, in the catalyst tower (4), CO and H 2 in the raw material air are converted into CO 2 and H 2 O by oxygen in the air.
Rinsing cooling tower that contacts the noble metal oxidation catalyst that oxidizes to high temperature and cools the air to near ambient temperature for the next process
(5) is introduced and cooled.
【００４２】続いて、吸着塔(7) にて、上記ＣＯ2 とＨ
2 Ｏとが、ＰＳＡ方式等のゼオライト等を充填した吸着
剤により除去され、流路Ｂを経て主熱交換器(8) へ導入
される。Subsequently, in the adsorption tower (7), the CO 2 and H
2 O is removed by an adsorbent filled with zeolite or the like of the PSA system or the like, and introduced into the main heat exchanger (8) via the flow path B.
【００４３】主熱交換器(8) では、原料空気は、冷熱を
供給する製品窒素ガスＥ＋還流窒素ガスＦ、廃ガス（Ｎ
2 ）Ｈおよび廃ガス（Ｏ2 ）Ｊと熱交換して冷却され、
冷却途中で後述する膨張タービン(13)への流路Ｃ2 を分
岐した後、冷端部ではほぼ飽和ガス温度の約−１６８℃
まで冷却され、流路Ｃ1 を経て単式精留塔(10)下部のコ
ンデンサー／リボイラー(11)へ送入され、単式精留塔(1
0)下部に貯留する約−１８０℃の液体酸素および微量の
液体アルゴンを加熱して再沸させると同時に、自らは過
冷却されて約−１７７℃に冷却される。In the main heat exchanger (8), the raw material air is supplied as product nitrogen gas E + reflux nitrogen gas F for supplying cold heat and waste gas (N
2 ) cooled by heat exchange with H and waste gas (O 2 ) J;
After branching the flow path C 2 to be described later expansion turbine (13) in the middle cooling, approximately about -168 ° C. a saturated gas temperature in the cold end
Until cooled, fed via the channel C 1 to simplex fractionator (10) bottom of the condenser / reboiler (11), single direction rectifying column (1
0) The liquid oxygen and a small amount of liquid argon at about -180 ° C stored in the lower part are heated and reboiled, and at the same time, they are supercooled and cooled to about -177 ° C.
【００４４】そして管路Ｄにより、直接単式精留塔(10)
中部へ送入される流路と、後述する粗アルゴン塔(12)お
よび精製アルゴン塔(23)の精留のための上部コンデンサ
ー経由で同じく単式精留塔(10)中部へ導入される流路と
に分岐され、それぞれＪ−Ｔ弁(JT)を経て約−１９２℃
までさらに冷却され、単式精留塔内(10)中部に送入さ
れ、精留、分離される。Then, through the line D, the single type rectification column (10)
The flow path sent to the central part, and the flow path also introduced into the central part of the single-type rectification column (10) via the upper condenser for rectification of the crude argon column (12) and the purified argon column (23) described below. And about -192 ° C via a JT valve (JT).
It is further cooled until it is sent into the middle part of the single-column rectification column (10), where it is rectified and separated.
【００４５】他方、流路Ｃ2 に分岐した原料空気は、膨
張タービン(13)に約−１４０℃で送入され、断熱膨張の
ための外部仕事として同軸の圧縮機(14)を起動させ、先
に述べた製品窒素ガスＥおよび還流窒素ガスＦをそれぞ
れ昇圧させることにより動力を回収してタービンより所
要の寒冷を発生させ、同タービン出口の空気温度を約−
１８５℃まで冷却する。そして膨張タービン(13)を出た
原料空気は、流路Ｃ3により液化・過冷却器(9) を経て
過冷却液体空気として単式精留塔(10)中部に送入され、
塔内で精留分離に供される。[0045] On the other hand, feed air is branched into the flow path C 2 is fed at about -140 ° C. in an expansion turbine (13), coaxial of the compressor (14) is activated as external work for adiabatic expansion, Power is recovered by increasing the pressure of the product nitrogen gas E and the reflux nitrogen gas F described above to generate required cooling from the turbine, and the air temperature at the turbine outlet is reduced by about-
Cool to 185 ° C. The feed air leaving the expansion turbine (13), single direction fractionator (10) as a supercooled liquid air through liquefaction and subcooling device (9) by the channel C 3 is fed to the middle,
It is subjected to rectification and separation in the column.
【００４６】還流液である液体窒素は、流路Ｇを経て単
式精留塔(10)頂部付近へ送入されるが、この液体窒素の
製造工程は、単式精留塔(10)頂部から排出される先述の
製品窒素ガスＥ＋還流窒素ガスＦが圧縮機(14)にて加圧
された後、還流窒素ガスＦを分岐して取り出し、主熱交
換器(8) で冷却され、液化・過冷却器(9) で過冷却さ
れ、一部は粗アルゴン塔(12)下部のリボイラーへ導入さ
れ、同塔下部の液体酸素に残存するアルゴンを再沸させ
るための加熱源となり、同時に自らは液体酸素等に冷却
され、再び合流してＪ−Ｔ弁(JT)を経由してさらに約−
１９４℃に冷却され、上述の通り流路Ｇを経て単式精留
塔(10)頂部付近より塔内へ送入、流下させて塔内中部へ
送入される液体空気等へ冷熱を与えて酸素等を液化さ
せ、塔内下部へ流下させ、同時に自らは気化ガスとなっ
て塔内を上昇し、製品窒素ガスＥおよび廃窒素ガスＨと
して単式精留塔(10)頂部付近より排出される。Liquid nitrogen, which is a reflux liquid, is sent to the vicinity of the top of the single-column rectification column (10) through a flow path G, and the liquid nitrogen is produced by discharging from the top of the single-column rectification column (10). After the above-mentioned product nitrogen gas E + reflux nitrogen gas F is pressurized by the compressor (14), the reflux nitrogen gas F is branched and taken out, cooled by the main heat exchanger (8), liquefied and cooled. It is supercooled by the cooler (9), and part of it is introduced into the reboiler below the crude argon column (12), and serves as a heating source for reboiling the argon remaining in the liquid oxygen at the bottom of the column. Cooled to oxygen, etc., merges again and passes through the J-T valve (JT) for approx.
It is cooled to 194 ° C. and sent into the tower from the vicinity of the top of the single-column rectification tower (10) via the flow path G as described above, and is cooled to give liquid air or the like which is sent to the middle part of the tower by oxygen and Are liquefied and flow down to the lower part of the tower, and at the same time, themselves become vaporized gas and rise in the tower, and are discharged as product nitrogen gas E and waste nitrogen gas H from the vicinity of the top of the single type rectification column (10).
【００４７】製品窒素ガスＥは、還流液の原料となる還
流窒素ガスＦと共に単式精留塔(10)頂部より抽出され、
約−１９４℃の冷熱を液化・過冷却器(9) に与え、続い
て主熱交換器(8) にて原料空気等に冷熱を与えた後、常
温に戻り、圧縮機(14)にて所要の圧力まで昇圧して製品
窒素ガスＥとし、その一部を分流させて前述還流窒素ガ
スＦとして取り出し、再び系内へ送入する。The product nitrogen gas E is extracted from the top of the single-column rectification column (10) together with the reflux nitrogen gas F which is a raw material of the reflux liquid.
The liquefaction / supercooler (9) is given cold heat of about -194 ° C, and then the raw material air is cooled by the main heat exchanger (8). The pressure is raised to a required pressure to produce product nitrogen gas E, a part of which is separated and taken out as the above-mentioned reflux nitrogen gas F, and sent again into the system.
【００４８】廃ガス（窒素）Ｈは、単式精留塔(10)上部
より流路Ｈを経て液化・過冷却器(9) に約−１９４℃の
冷熱を与え、続いて主熱交換器(8) に冷熱を与えた後、
常温に戻り、そのうち一部を分岐して吸着塔(7) の再生
ガスとして使用した後、大気放出される。また、他の一
部は水洗冷却塔(5) の冷却用循環水を冷却するための蒸
発冷却塔(6) へ送入され、同循環水の蒸発を促進して蒸
発潜熱を発生させた後、大気放出される。The waste gas (nitrogen) H is supplied from the upper part of the single-column rectification column (10) to the liquefaction / supercooler (9) through the flow path H to give a cooling heat of about -194 ° C., and then the main heat exchanger (10). 8) After applying cold to
After returning to normal temperature, a part of it is branched and used as a regeneration gas for the adsorption tower (7), and then released to the atmosphere. Another part is sent to the evaporative cooling tower (6) for cooling the circulating water for cooling in the rinsing cooling tower (5), which promotes the evaporation of the circulating water to generate latent heat of evaporation. Released to the atmosphere.
【００４９】廃ガス（酸素）Ｊは、単式精留塔(10)底部
の液体酸素と同塔下部ガス層より気体酸素をそれぞれ抽
出し、液化・過冷却器(9) へ約−１８０℃の冷熱を与え
た後に合流して流路Ｊを経て主熱交換器(8) へ冷熱を供
給し、常温に戻って廃ガスとして大気放出されるか、ま
たは製品酸素ガスとして回収される。The waste gas (oxygen) J is obtained by extracting liquid oxygen at the bottom of the single-column rectification column (10) and gaseous oxygen from the lower gas layer of the single-column rectification column (10). After applying the cold heat, they are merged and supplied to the main heat exchanger (8) via the flow path J, and then returned to room temperature and released to the atmosphere as waste gas or recovered as product oxygen gas.
【００５０】循環酸素は、流路Ｉを経て単式精留塔(10)
下部に溜まった液体酸素を抽出し、液化・過冷却器(9)
に冷熱を与えた後、単式精留塔(10)中部へ送入される。
その流路Ｉには同塔下部の液体酸素液面を保持するため
の液面調節弁(17)を設け、これを液面指示計(16)により
制御する。これは、単式精留塔(10)コンデンサー／リボ
イラー(11)の効果を維持して原料空気を液化・過冷却す
ると共に、液体酸素中に残存するアルゴンを再沸させて
同ガス回収率を改善すること、また、比較的下部より循
環液体酸素を抽出し溶存アルゴンを含む酸素ガスを単式
精留塔(10)中部へ送入することによりアルゴン回収率の
向上を促進できる。さらに、粗アルゴン塔(12)の頂部よ
り凝縮しきれない微量のアルゴンを含む凝縮ガス（窒素
等）を抽出し、単式精留塔(10)へ送入することにより、
上記と同様にアルゴン回収率向上を図ることができる。The circulating oxygen passes through the channel I through the single rectification column (10).
Extracts liquid oxygen accumulated at the bottom, liquefies and supercools (9)
, And then sent to the central part of the single rectification column (10).
The flow path I is provided with a liquid level control valve (17) for maintaining the liquid oxygen liquid level at the lower part of the tower, and this is controlled by a liquid level indicator (16). This means that the raw air is liquefied and supercooled while maintaining the effects of the single-column rectification tower (10) condenser / reboiler (11), and argon remaining in the liquid oxygen is reboiled to improve the gas recovery rate. Further, by extracting circulating liquid oxygen from a relatively lower portion and sending oxygen gas containing dissolved argon into the central portion of the single-column rectification column (10), an improvement in the argon recovery rate can be promoted. Furthermore, by extracting a condensed gas (such as nitrogen) containing a trace amount of argon that cannot be condensed from the top of the crude argon column (12) and sending it to the single-column rectification column (10),
As described above, the argon recovery rate can be improved.
【００５１】ＬＮ2 （液体窒素）タンク（コールドエバ
ポレーター）(18)は、停電時等のバックアップ用とし
て、また装置再起動時の立上げ時間短縮用として設置し
たもので、前者はＬＮ2 タンク(18)の自圧により液体窒
素を空温式蒸発器に圧送・気化させて自動切換装置によ
り、窒素ガスを安定供給できる機能を有し、また、後者
はＬＮ2 （液体窒素）ポンプ(19)により系内へ寒冷源と
して直接圧送することにより、装置の立上げ時間を短縮
することができる。The LN 2 (liquid nitrogen) tank (cold evaporator) (18) is installed for backup in the event of a power failure or for shortening the startup time when the apparatus is restarted. The former is an LN 2 tank (cold evaporator). 18) has a function to supply and vaporize liquid nitrogen to an air-heated evaporator by its own pressure and to supply nitrogen gas stably by an automatic switching device. The latter is an LN 2 (liquid nitrogen) pump (19) As a result, the pressure can be directly fed into the system as a cold source, thereby shortening the startup time of the apparatus.
【００５２】粗アルゴン塔(12)下部にはリボイラー(12
a) を設け、そのリボイラー(12a) 管外に貯留される凝
縮液を制御するために、粗アルゴン塔(12)の底部から単
式精留塔(10)への流路に設けた液面調節弁(21)を、粗ア
ルゴン塔(12)下部に設けた液面指示計(20)により制御す
る。このようにすると、粗アルゴン塔(12)下部に溜まる
液体酸素中に残存するアルゴンを再沸させることによ
り、アルゴン回収率を高めることができる上、装置停止
時に同塔内の液面を保持しておくことにより塔内の精留
条件が整いやすくなり、再起動時の立上げ時間を短縮す
ることができる。At the bottom of the crude argon tower (12), a reboiler (12
a), and in order to control the condensate stored outside the reboiler (12a), the liquid level control provided in the flow path from the bottom of the crude argon tower (12) to the single-type rectification tower (10) The valve (21) is controlled by a liquid level indicator (20) provided below the crude argon column (12). In this way, the argon remaining in the liquid oxygen stored in the lower portion of the crude argon column (12) can be reboiled to increase the argon recovery rate, and the liquid level in the column can be maintained when the apparatus is stopped. By doing so, the rectification conditions in the tower can be easily adjusted, and the startup time at the time of restart can be shortened.
【００５３】粗アルゴン塔(12)上部からの粗アルゴンガ
スは精製アルゴン塔(23)に導入され、精製アルゴン塔(2
3)上部コンデンサー内の冷媒の液体空気により、沸点の
高いアルゴンは液化して塔下部に向けて流下し、塔底部
から製品高純度液体アルゴンとして採取される。液化し
ない窒素ガスや過剰に添加された水素ガスは、精製アル
ゴン塔(23)の頂部より放出され、熱交換後大気に廃棄さ
れる。The crude argon gas from the upper part of the crude argon column (12) is introduced into the purified argon column (23),
3) Argon having a high boiling point is liquefied by the liquid air of the refrigerant in the upper condenser, flows down toward the bottom of the tower, and is collected as product high-purity liquid argon from the bottom of the tower. Non-liquefied nitrogen gas and excessively added hydrogen gas are discharged from the top of the refined argon column (23), and are discarded to the atmosphere after heat exchange.
【００５４】実施例２ 図２は、本発明に基く高純度窒素ガスおよび高純度液体
アルゴンの製造工程の他の一例を示した要部のフローシ
ートである。Example 2 FIG. 2 is a flow sheet of a main part showing another example of the process for producing high-purity nitrogen gas and high-purity liquid argon based on the present invention.
【００５５】この実施例２においては、流路Ｃ2 に分岐
した原料空気を膨張タービン(13)に送入してから、流路
Ｃ3 により直接単式精留塔(10)中部に送入し、また流路
Ｃ1の原料空気は、液化・過冷却器(9) を経て単式精留
塔(10)下のコンデンサー／リボイラー(11)に送入するよ
うにしてある。In the second embodiment, after the raw material air branched into the flow path C 2 is fed into the expansion turbine (13), it is directly fed into the central part of the single type rectification tower (10) through the flow path C 3. and air feed flow path C 1 is simplex fractionator (10) through liquefaction and subcooling device (9) are to be fed to the condenser / reboiler (11) below.
【００５６】[0056]
【発明の効果】本発明によれば、空気の分離を単式精留
塔を用いて行うと共に、低圧力下での精留、製品窒素ガ
スの一部を再液化した還流液の利用、製品としては採取
不要な液体酸素の保持する寒冷エネルギーの利用などを
配慮しているので、液体アルゴンの高収率取得、電力原
単位の低減、立上げ時間の短縮、各機器の単純化と装置
製作コストの低減を図ることができ、高純度窒素ガスお
よび高純度液体アルゴンを工業的に有利に製造すること
ができる。According to the present invention, air is separated using a single type of rectification column, rectification under a low pressure, use of a reflux liquid obtained by reliquefying a part of product nitrogen gas, and Considers the use of cold energy that holds liquid oxygen that does not need to be collected, so that a high yield of liquid argon can be obtained, the power consumption can be reduced, the start-up time can be shortened, the equipment can be simplified, and equipment manufacturing costs can be reduced. , And high-purity nitrogen gas and high-purity liquid argon can be industrially advantageously produced.
【図１】本発明に基く高純度窒素ガスおよび高純度液体
アルゴンの製造工程の一例を示したフローシートであ
る。FIG. 1 is a flow sheet showing an example of a process for producing high-purity nitrogen gas and high-purity liquid argon based on the present invention.
【図２】本発明に基く高純度窒素ガスおよび高純度液体
アルゴンの製造工程の他の一例を示した要部のフローシ
ートである。FIG. 2 is a main part flow sheet showing another example of the production process of high-purity nitrogen gas and high-purity liquid argon based on the present invention.
(1) …吸入塔、 (2) …フィルター、 (3) …空気圧縮機、 (4) …触媒塔、 (5) …水洗冷却塔、 (6) …蒸発冷却塔、 (7) …吸着塔、 (8) …主熱交換器、 (9) …液化・過冷却器、 (10)…単式精留塔、 (11)…コンデンサー／リボイラー、 (12)…粗アルゴン塔、(12a) …リボイラー、 (13)…膨張タービン、 (14)…圧縮機、 (15)…コールドボックス、 (16)…液面指示計、 (17)…液面調節弁、 (18)…ＬＮ2 （液体窒素）タンク、 (19)…ＬＮ2 （液体窒素）ポンプ、 (20)…液面指示計、 (21)…液面調節弁、 (22)…アルゴン精製装置、 (23)…精製アルゴン塔、 (JT)…Ｊ−Ｔ弁、 Ａ〜Ｊ…流路(1) ... Suction tower, (2) ... Filter, (3) ... Air compressor, (4) ... Catalyst tower, (5) ... Washing cooling tower, (6) ... Evaporation cooling tower, (7) ... Adsorption tower , (8)… Main heat exchanger, (9)… Liquefaction / supercooler, (10)… Single rectification column, (11)… Condenser / reboiler, (12)… Crude argon column, (12a)… Reboiler , (13) expansion turbine, (14) compressor, (15) cold box, (16) liquid level indicator, (17) liquid level control valve, (18) LN 2 (liquid nitrogen) Tank, (19) LN 2 (liquid nitrogen) pump, (20) liquid level indicator, (21) liquid level control valve, (22) argon purifier, (23) purified argon tower, (JT ) ... JT valve, A to J ... Flow path
フロントページの続き (56)参考文献 特開 昭61−289284（ＪＰ，Ａ) 特開 平５−45051（ＪＰ，Ａ) 特開 平６−273035（ＪＰ，Ａ) 特開 昭59−90613（ＪＰ，Ａ) 特開 平８−61844（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) F25J 1/00 - 5/00 C01B 21/02 C01B 23/00 Continuation of the front page (56) References JP-A-61-289284 (JP, A) JP-A-5-45051 (JP, A) JP-A-6-273035 (JP, A) JP-A-59-90613 (JP, A) , A) JP-A-8-61844 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) F25J 1/00-5/00 C01B 21/02 C01B 23/00
Claims (2)
り、製品として、高純度窒素ガスおよび高純度液体アル
ゴンを得る方法であって、 精留塔として単式精留塔(10)を用いること、’単式精留塔(10)における精留を、 0.1〜 0.5 kg/cm
2 Gの低圧条件下に行うこと、 単式精留塔(10)の下部に生成する液体酸素について
は、その全部または大部分を系の主たる冷源として使用
すること、’このとき、単式精留塔(10)の下部に溜まる液体酸素
を、その一部については、液化・過冷却器(9) の冷媒と
して使用して液体酸素が保有している寒冷エネルギーを
利用した後に、単式精留塔(10)中段のアルゴン濃縮層上
部に返送し、他部については、液化・過冷却器(9) の冷
媒として使用した後、主熱交換器(8) に導入して原料空
気の冷媒として使用してから、最終的に冷熱を喪失して
気化した廃酸素ガスとして大気に放出すること、 単式精留塔(10)の頂部に生成する高純度窒素ガスにつ
いては、その大部分を冷源として使用した後に製品とし
ての高純度窒素ガスとして取り出すこと、 単式精留塔(10)の中間部に生成するアルゴン濃縮ガス
層については、それを粗アルゴン塔(12)を経てアルゴン
精製装置(22)、さらには精製アルゴン塔(23)に導き、製
品としての高純度液体アルゴンを得ること、および、 ’粗アルゴン塔(12)下部にリボイラー(12a) を設ける
と共に、そのリボイラー(12a) 管外に貯留される凝縮液
を制御するために、粗アルゴン塔(12)の底部から単式精
留塔(10)への流路に設けた液面調節弁(21)を、粗アルゴ
ン塔(12)下部に設けた液面指示計(20)により制御するよ
うにしたこと、 を特徴とする空気からの窒素およびアルゴンの製造方
法。(1) A raw air is rectified by a rectification column.
High purity nitrogen gas and high purity liquid
A method for obtaining a gon, wherein a single-type rectification column (10) is used as the rectification column,'' The rectification in the single-column rectification tower (10) is 0.1 to 0.5 kg / cm
Two G under low pressure conditions, Liquid oxygen generated at the lower part of the single rectification column (10)
Uses all or most of it as the main cold source of the system
To do,'At this time, liquid oxygen collected at the bottom of the single-column rectification column (10)
And partly with the refrigerant in the liquefaction / supercooler (9).
To use the cold energy held by liquid oxygen
After use, on the argon concentration layer in the middle stage of the single-column rectification column (10)
To the liquefier / supercooler (9).
After being used as a medium, it is introduced into the main heat exchanger (8) to
And finally loses cold heat
Release it to the atmosphere as vaporized waste oxygen gas, The high-purity nitrogen gas generated at the top of the
Most of them are used as cold sources before they become products.
As high-purity nitrogen gasthing, Argon-enriched gas generated in the middle part of the single rectification column (10)
For the layer, pass it through a crude argon column (12)
It is led to the purification device (22) and further to the purification argon tower (23),
Obtaining high-purity liquid argon as a product,and, '' Install a reboiler (12a) below the crude argon tower (12)
Condensate stored outside the reboiler (12a)
From the bottom of the crude argon column (12) to control
The liquid level control valve (21) provided in the flow path to the distillation tower (10) is
It is controlled by a liquid level indicator (20) provided at the bottom of the
What happened, For producing nitrogen and argon from air characterized by
Law.
り、製品として、高純度窒素ガスおよび高純度液体アル
ゴンを得るための装置であって、 精留塔が単式精留塔(10)であること、 単式精留塔(10)の下部に生成する液体酸素の全部また
は大部分を、主熱交換器(8) および液化・過冷却器(9)
を含む系の主たる冷源として使用するための管路を備え
ていること、’このとき、単式精留塔(10)の下部に溜まる液体酸素
を、その一部については、液化・過冷却器(9) の冷媒と
して使用して液体酸素が保有している寒冷エネルギーを
利用した後に、単式精留塔(10)中段のアルゴン濃縮層上
部に返送し、他部については、液化・過冷却器(9) の冷
媒として使用した後、主熱交換器(8) に導入して原料空
気の冷媒として使用してから、最終的に冷熱を喪失して
気化した廃酸素ガスとして大気に放出するための管路を
それぞれ備えていること、 単式精留塔(10)の頂部に生成する高純度窒素ガスの大
部分を系内の冷源として使用した後に製品としての高純
度窒素ガスとして取り出すための管路を備えているこ
と、 単式精留塔(10)の中間部に生成するアルゴン濃縮ガス
層を蒸留して粗アルゴンを得るための粗アルゴン塔(12)
と、粗アルゴン中の酸素を除去するためのアルゴン精製
装置(22)と、酸素が除去された変成アルゴンを精留して
高純度液体アルゴンを得るための精製アルゴン塔(23)と
を備えていること、および、 ’粗アルゴン塔(12)下部にリボイラー(12a) を設ける
と共に、そのリボイラー(12a) 管外に貯留される凝縮液
を制御するために、粗アルゴン塔(12)の底部から単式精
留塔(10)への流路に液面調節弁(21)を設け、かつその液
面調節弁(21)を制御するめの液面指示計(20)を粗アルゴ
ン塔(12)下部に設けたこと、 を特徴とする空気からの窒素およびアルゴンの製造装
置。2. A method for rectifying raw material air in a rectification column.
High purity nitrogen gas and high purity liquid
A device for obtaining a gon, wherein the rectification column is a single-stage rectification column (10), and all of the liquid oxygen generated at the bottom of the single-stage rectification column (10) or
Consists mostly of a main heat exchanger (8) and a liquefaction / supercooler (9)
Equipped with a pipeline for use as the main cold source for systems containing
That'At this time, liquid oxygen collected at the bottom of the single-column rectification column (10)
And partly with the refrigerant in the liquefaction / supercooler (9).
To use the cold energy held by liquid oxygen
After use, on the argon concentration layer in the middle stage of the single-column rectification column (10)
To the liquefier / supercooler (9).
After being used as a medium, it is introduced into the main heat exchanger (8) to
And finally loses cold heat
A pipe for discharging to the atmosphere as vaporized waste oxygen gas
Have each, Large amount of high-purity nitrogen gas generated at the top of the single rectification column (10)
After using the part as a cold source in the system, high purity as a product
Equipped with a conduit for extracting nitrogen gasThis
When, Argon-enriched gas generated in the middle part of the single rectification column (10)
Crude argon column for distillation of the layer to obtain crude argon (12)
And argon purification to remove oxygen in crude argon
The apparatus (22) is rectified with deoxygenated oxygen from which oxygen has been removed.
Purified argon column (23) to obtain high purity liquid argon
Having,and, '' Install a reboiler (12a) below the crude argon tower (12)
Condensate stored outside the reboiler (12a)
From the bottom of the crude argon column (12) to control
Provide a liquid level control valve (21) in the flow path to the distillation tower (10), and
The liquid level indicator (20) for controlling the level control valve (21)
Installed at the bottom of the tower (12), For producing nitrogen and argon from air characterized by the following:
Place.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34483997A JP3181546B2 (en) | 1997-12-15 | 1997-12-15 | Method and apparatus for producing nitrogen and argon from air |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34483997A JP3181546B2 (en) | 1997-12-15 | 1997-12-15 | Method and apparatus for producing nitrogen and argon from air |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11173753A JPH11173753A (en) | 1999-07-02 |
| JP3181546B2 true JP3181546B2 (en) | 2001-07-03 |
Family
ID=18372382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34483997A Expired - Fee Related JP3181546B2 (en) | 1997-12-15 | 1997-12-15 | Method and apparatus for producing nitrogen and argon from air |
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| Country | Link |
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| JP4577977B2 (en) * | 2000-11-14 | 2010-11-10 | 大陽日酸株式会社 | Air liquefaction separation method and apparatus |
| FR2957408B1 (en) | 2010-03-09 | 2015-07-17 | Air Liquide | METHOD AND APPARATUS FOR HEATING AN AIR GAS FROM AN AIR SEPARATION APPARATUS |
| JP6440232B1 (en) * | 2018-03-20 | 2018-12-19 | レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | Product nitrogen gas and product argon production method and production apparatus thereof |
| JP7133735B1 (en) * | 2022-03-07 | 2022-09-08 | レール・リキード－ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | air separator |
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