JPH09110406A - Neon and helium manufacturing method - Google Patents
Neon and helium manufacturing methodInfo
- Publication number
- JPH09110406A JPH09110406A JP7286606A JP28660695A JPH09110406A JP H09110406 A JPH09110406 A JP H09110406A JP 7286606 A JP7286606 A JP 7286606A JP 28660695 A JP28660695 A JP 28660695A JP H09110406 A JPH09110406 A JP H09110406A
- Authority
- JP
- Japan
- Prior art keywords
- neon
- nitrogen
- gas
- helium
- tower
- 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.)
- Granted
Links
- 229910052754 neon Inorganic materials 0.000 title claims abstract description 172
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 239000001307 helium Substances 0.000 title claims abstract description 83
- 229910052734 helium Inorganic materials 0.000 title claims abstract description 83
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 title description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 222
- 239000007789 gas Substances 0.000 claims abstract description 129
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 107
- 238000000034 method Methods 0.000 claims abstract description 58
- 239000001257 hydrogen Substances 0.000 claims abstract description 49
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001179 sorption measurement Methods 0.000 claims abstract description 33
- 238000000926 separation method Methods 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010457 zeolite Substances 0.000 claims abstract description 13
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 9
- 238000009833 condensation Methods 0.000 claims abstract description 7
- 230000005494 condensation Effects 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 description 38
- 238000010926 purge Methods 0.000 description 22
- 239000007788 liquid Substances 0.000 description 16
- 150000002431 hydrogen Chemical class 0.000 description 15
- 238000011084 recovery Methods 0.000 description 15
- 230000008929 regeneration Effects 0.000 description 13
- 238000011069 regeneration method Methods 0.000 description 13
- 239000003463 adsorbent Substances 0.000 description 10
- 238000009413 insulation Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002826 coolant Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000006837 decompression Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000009189 diving Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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
- F25J3/04624—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 integrated mass and heat exchange, so-called non-adiabatic rectification, e.g. dephlegmator, reflux exchanger
-
- 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
-
- 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
- F25J2200/32—Processes or apparatus using separation by rectification using a side column fed by a stream from the 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
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
-
- 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
- F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
-
- 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
- F25J2215/30—Helium
-
- 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
- F25J2215/32—Neon
-
- 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
- F25J2290/62—Details of storing a fluid in a tank
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Separation Of Gases By Adsorption (AREA)
- Separation By Low-Temperature Treatments (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
(57)【要約】
【課題】 空気分離装置の下部精留塔上部からの放出ガ
スから凝縮分離操作によって窒素を除去したのち、ＰＳ
Ａ法のみで連続的に高純度ネオン、高純度ヘリウムを得
る。
【解決手段】 空気分離装置の下部精留塔上部からの放
出ガス、すなわちネオン、ヘリウム、水素を含む窒素ガ
スから凝縮分離操作で大部分の窒素を除去する工程と、
合成ゼオライトを用いた常温圧力変動式吸着法によって
残留する窒素を除去する工程と、活性炭を用いた−１０
０℃以下の低温圧力変動式吸着法によって水素を除去し
てネオンとヘリウムを分離する工程とからなる。
(57) Abstract: Nitrogen is removed from a gas discharged from an upper part of a lower rectification column of an air separation device by a condensation separation operation, and then PS
High-purity neon and high-purity helium are continuously obtained only by the method A. SOLUTION: A step of removing most of nitrogen from a gas released from an upper part of a lower rectification column of an air separation device, that is, a nitrogen gas containing neon, helium and hydrogen by a condensation separation operation,
A step of removing residual nitrogen by a room temperature pressure swing adsorption method using synthetic zeolite, and -10 using activated carbon.
The process comprises the steps of removing hydrogen and separating neon and helium by a low temperature pressure fluctuation adsorption method at 0 ° C. or less.
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、空気分離装置の
放出ガスを原料としてネオン、ヘリウムを圧力変動式吸
着法（以下ＰＳＡ法という）を主体としたプロセスで製
造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing neon and helium from a gas discharged from an air separation device as a raw material by a process mainly including a pressure swing adsorption method (hereinafter referred to as PSA method).
【０００２】[0002]
【従来の技術】ネオンは、空気中に１８．１８ｐｐｍ含
まれており、放電管用封入ガスとして用いられる。空気
を液化蒸留して酸素、窒素、アルゴンを製造する際に
は、通常、窒素より沸点の低いヘリウム、ネオン、水素
等は凝縮されないガスとして下部精留塔上部から放出ガ
ス（通常ヘリウム抜きと称す）として放出される。この
放出ガスの組成は、ガス放出量によって変化するが、ネ
オン＋ヘリウムが０．５％、水素が０．０５％程度が含
有されており、残りは窒素である。一般にネオンを製造
する場合は、空気分離装置の下部精留塔上部からの放出
ガスを原料とし、蒸留法または温度変動式吸着法（以下
ＴＳＡという）によって製造されている。2. Description of the Related Art Neon is contained in air at 18.18 ppm and is used as a filling gas for a discharge tube. When liquefying air to produce oxygen, nitrogen, and argon, helium, neon, hydrogen, etc., which have a lower boiling point than nitrogen, are usually released as gas not condensed from the upper part of the lower rectification column (usually called helium removal). ) Is released as. The composition of the released gas changes depending on the amount of released gas, but contains 0.5% of neon + helium, 0.05% of hydrogen, and the rest is nitrogen. Generally, neon is produced by a distillation method or a temperature fluctuation adsorption method (hereinafter referred to as TSA) using a gas released from an upper portion of a lower rectification column of an air separation device as a raw material.
【０００３】ヘリウムは、空気中に５．２４ｐｐｍ存在
するが、用途は極低温冷媒、溶接用保護ガス、光ファイ
バー製造時のシールガス、気球用充填ガス、潜水用人工
空気、クロマトグラフィーのキャリヤーガス、化学反応
用の不活性ガス、放電管用封入ガスなどである。ヘリウ
ムは、現在コスト的な問題から、空気分離装置の副生ガ
スとしては製造されず、すべて天然ガスから製造されて
いる。Helium is present at 5.24 ppm in the air, but its applications are cryogenic refrigerants, protective gas for welding, seal gas at the time of optical fiber manufacturing, balloon filling gas, artificial air for diving, carrier gas for chromatography, For example, an inert gas for a chemical reaction and a filling gas for a discharge tube. Due to cost issues, helium is not currently produced as a by-product gas for air separation units, but is produced entirely from natural gas.
【０００４】空気分離装置の下部精留塔上部からの放出
ガスを原料とするネオンの公知の製造方法としては、圧
力約５ｋｇｆ／ｃｍ2・Ｇで抜出される放出ガスを大気
圧の液体窒素で冷却することにより大部分の窒素を凝縮
分離し、ネオン４０〜５０ｍｏｌ．％、ヘリウム２０〜
２５ｍｏｌ．％、水素３〜５ｍｏｌ．％、残り窒素の濃
縮ガスとする。ついでこの濃縮ガス中の水素は、過剰の
酸素で触媒燃焼せしめて水に変換し、生成した水を除去
したのち、ＴＳＡ法で過剰酸素分と残存窒素とを除去
し、ネオン、ヘリウム混合ガスとする。さらにネオンの
液化点付近の温度下で深冷分離するか、液体窒素程度の
温度下で吸着分離してネオン、ヘリウムをそれぞれ回収
している。As a known method for producing neon from the gas discharged from the upper part of the lower rectification column of the air separation device, the gas discharged at a pressure of about 5 kgf / cm 2 · G is liquid nitrogen at atmospheric pressure. Most of the nitrogen was condensed and separated by cooling, and neon 40-50 mol. %, Helium 20 ~
25 mol. %, Hydrogen 3-5 mol. %, The remaining nitrogen is a concentrated gas. Then, the hydrogen in the concentrated gas is catalytically burned with excess oxygen to be converted into water, and the generated water is removed. Then, the excess oxygen content and the residual nitrogen are removed by the TSA method to obtain a mixed gas of neon and helium. To do. Further, neon and helium are respectively collected by deep-chill separation at a temperature near the liquefaction point of neon or by adsorption separation at a temperature of about liquid nitrogen.
【０００５】上記の分離法では、水素除去用として触媒
法を用いているため、装置が複雑となっていると共に、
ＴＳＡ法を用いているため、熱損失の問題点が有り、コ
ストが高くなる要因となっている。さらに、ヘリウム、
ネオンの分離に深冷分離法を用いた場合は、２０°Ｋ程
度の低温が必要なことから、技術的に容易でない。In the above separation method, since the catalytic method is used for removing hydrogen, the apparatus is complicated and
Since the TSA method is used, there is a problem of heat loss, which causes a cost increase. In addition, helium,
When the cryogenic separation method is used for separating neon, a low temperature of about 20 ° K is required, which is technically not easy.
【０００６】液体窒素程度の低温下での吸着法を用いた
ヘリウム、ネオンの分離法としては、空気分離装置の下
部精留塔上部からの放出ガスを温度６７〜７７°Ｋ、圧
力４〜７ｋｇｆ／ｃｍ2・Ｇにおいて２段階で分縮する
ことにより窒素を除去し、ネオン６８〜７４Ｖｏｌ．
％、ヘリウム２２〜７４Ｖｏｌ．％、水素１．５〜２Ｖ
ｏｌ．％、窒素１〜８Ｖｏｌ．％および痕跡量の酸素と
炭化水素類を含有する混合物となし、この混合物を細孔
径８Å〜９Åの微孔性吸着剤に４〜７ｋｇｆ／ｃｍ2・
Ｇの圧力で通過させて残留窒素、酸素、水素および炭化
水素類を吸着させ、次に混合物の圧力を４〜７ｋｇｆ／
ｃｍ2・Ｇから１０-1〜１０-2ｍｍＨｇ以下に徐々に減
圧させることによって吸着剤から窒素、酸素、水素およ
び炭化水素類を脱着させる。この吸脱着を液体窒素によ
って温度調節した微孔性吸着剤によって行う方法（特開
昭５１−１０４４９７号公報）が提案されている。As a method of separating helium and neon using an adsorption method at a temperature as low as liquid nitrogen, the gas discharged from the upper part of the lower rectification column of the air separation device is at a temperature of 67 to 77 ° K and a pressure of 4 to 7 kgf. / Cm 2 · G to reduce nitrogen by concentrating in two steps, neon 68-74 Vol.
%, Helium 22 to 74 Vol. %, Hydrogen 1.5-2V
ol. %, Nitrogen 1 to 8 Vol. % And trace amounts of oxygen and hydrocarbons as a mixture, and this mixture was applied to a microporous adsorbent having a pore size of 8Å to 9Å at 4 to 7 kgf / cm 2 ·.
It is passed at a pressure of G to adsorb residual nitrogen, oxygen, hydrogen and hydrocarbons, then the pressure of the mixture is 4 to 7 kgf /
Nitrogen, oxygen, hydrogen and hydrocarbons are desorbed from the adsorbent by gradually reducing the pressure from cm 2 · G to 10 −1 to 10 −2 mmHg or less. A method has been proposed in which this adsorption / desorption is carried out by a microporous adsorbent whose temperature is controlled by liquid nitrogen (JP-A-51-104497).
【０００７】潜水呼吸ガスから希ガスのヘリウムまたは
ネオンあるいはその両方を回収するのに、炭素分子ふる
いを吸着剤とする常温ＰＳＡで精製する方法（特公平３
−７２５６６号公報）が提案されている。In order to recover rare gas helium and / or neon from diving breathing gas, a method of purification with room temperature PSA using a carbon molecular sieve as an adsorbent (Patent Publication 3)
-72566) is proposed.
【０００８】さらに、他の方法としては、空気分離装置
の下部精留塔上部からの放出ガスを液体窒素で冷却し、
大部分の窒素を凝縮分離して窒素および水素を含むネオ
ン、ヘリウムの濃縮ガスとする工程と、得られた濃縮ガ
スを活性炭等の吸着剤が充填され、かつ−５０℃以下の
一定温度に冷却された吸着管の入口端から導入し、出口
端からヘリウムを導出させる工程と、濃縮ガス中のヘリ
ウムを少なくとも５ｍｏｌ％吸着管内に残留せしめて前
記濃縮ガスの導入を停止する工程、および前記温度を維
持しつつ置換ガスを入口端より導入し、出口端より順次
導出されるヘリウム、ネオンを分別採取する工程とから
なる方法（特開昭６３−６９７０３号公報）が提案され
ている。Further, as another method, the gas discharged from the upper part of the lower rectification column of the air separation device is cooled with liquid nitrogen,
A step of condensing and separating most of the nitrogen to obtain a concentrated gas of neon and helium containing nitrogen and hydrogen, and cooling the obtained concentrated gas to a constant temperature of -50 ° C or less filled with an adsorbent such as activated carbon. Of the helium from the inlet end of the adsorbed tube, and helium from the outlet end of the adsorbed tube, the step of leaving the helium in the concentrated gas at least 5 mol% in the adsorption tube to stop the introduction of the concentrated gas, and the temperature A method (JP-A-63-69703) has been proposed which comprises a step of introducing a replacement gas from the inlet end while maintaining it, and separately collecting helium and neon which are sequentially discharged from the outlet end.
【０００９】[0009]
【発明が解決しようとする課題】上記特開昭５１−１０
４４９７号公報に開示の方法は、空気分離装置の下部精
留塔上部からの放出ガスから２段階の分縮操作を用いて
窒素を除去しているため、比較的窒素濃度の低い濃縮ガ
スが得られるので、残留する窒素と水素の除去がＰＳＡ
法で可能である。このＰＳＡ操作で得られたネオン、ヘ
リウムの分離は、蒸留法あるいはＴＳＡ法による。この
ため、この方法は、２段階の分縮操作、ＰＳＡ操作でネ
オンとヘリウムとの混合ガスを製造するものであり、ネ
オンとヘリウムの分離は考慮されていない。また、特公
平３−７２５６６号公報に開示の方法も、同様にネオン
とヘリウムの混合ガスを製造するものであり、ネオンと
ヘリウム、水素の分離は考慮されていない。SUMMARY OF THE INVENTION The above-mentioned JP-A-51-10
In the method disclosed in Japanese Patent No. 4497, nitrogen is removed from the gas discharged from the upper part of the lower rectification column of the air separation device by using a two-stage partial condensation operation, so that a concentrated gas having a relatively low nitrogen concentration can be obtained. The removal of residual nitrogen and hydrogen is
It is possible by law. Separation of neon and helium obtained by this PSA operation is carried out by the distillation method or TSA method. Therefore, this method produces a mixed gas of neon and helium by a two-step decondensation operation and a PSA operation, and the separation of neon and helium is not considered. The method disclosed in Japanese Patent Publication No. 3-72566 also produces a mixed gas of neon and helium in the same manner, and does not consider separation of neon, helium and hydrogen.
【００１０】また、特開昭６３−６９７０３号公報に開
示の方法は、−５０℃以下の低温状態で吸着塔に濃縮ガ
ス中の窒素および置換ガスとしての窒素を導入するた
め、同一吸着温度のみで連続操業を行うことは不可能で
ある。すなわち、同一温度条件で減圧するのみでは、吸
着されている窒素が完全に脱着できず、繰り返し使用す
ることによって、高純度ネオンの製造ができない。この
ため、連続操業する場合は、加熱再生を行う必要がある
が明記されておらず実用的でない。しかも、この方法
は、ガスクロマトグラフ的分離法であるため、実験室で
行うには適していても、工業的規模で行うには適してい
ないと考える。Further, in the method disclosed in JP-A-63-69703, since nitrogen in the concentrated gas and nitrogen as a replacement gas are introduced into the adsorption tower at a low temperature of -50 ° C. or lower, only the same adsorption temperature is obtained. It is impossible to carry out continuous operations at. That is, adsorbed nitrogen cannot be completely desorbed only by reducing the pressure under the same temperature condition, and high-purity neon cannot be produced by repeated use. For this reason, in the case of continuous operation, it is necessary to perform heat regeneration, but it is not specified and not practical. Moreover, since this method is a gas chromatographic separation method, it is considered to be not suitable to be carried out on an industrial scale even though it is suitable to be carried out in a laboratory.
【００１１】この発明の目的は、空気分離装置の下部精
留塔上部からの放出ガスから凝縮分離操作によって窒素
を除去したのち、ＰＳＡ法のみで連続的に高純度ネオ
ン、高純度ヘリウムを分離、製造することができるネオ
ン、ヘリウムの製造方法を提供することにある。An object of the present invention is to remove nitrogen from a gas discharged from an upper part of a lower rectification column of an air separator by a condensation separation operation, and then continuously separate high-purity neon and high-purity helium only by a PSA method. It is to provide a method for producing neon and helium that can be produced.
【００１２】[0012]
【課題を解決するための手段】本発明者らは、上記目的
を達成すべく鋭意試験研究を行った。その結果、空気分
離装置の下部精留塔上部からの放出ガスから凝縮分離操
作によって窒素を除去し、（ネオン＋ヘリウム）６０
％、水素５％、窒素３５％程度の濃縮ガスとなし、濃縮
ガス中の窒素をＰＳＡ法によって除去してネオン、ヘリ
ウムおよび水素の混合ガスとする。この混合ガスは、ヘ
リウムを吸着せず、ネオン、水素を吸着し、かつ減圧に
よって容易にネオンが脱着すると共に、高真空とするこ
とによって水素を脱着する条件の低温ＰＳＡ法を用いて
分離することにより、同時に高純度ネオン、高純度ヘリ
ウムが製造できることを究明し、この発明に到達した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object. As a result, nitrogen was removed from the gas discharged from the upper part of the lower rectification column of the air separation device by a condensation separation operation, and (neon + helium) 60
%, Hydrogen 5%, nitrogen 35%, and nitrogen gas in the concentrated gas is removed by the PSA method to obtain a mixed gas of neon, helium, and hydrogen. This mixed gas does not adsorb helium, adsorbs neon and hydrogen, and is easily desorbed by depressurization, and is separated by using a low-temperature PSA method under which hydrogen is desorbed by applying a high vacuum. In this way, it was clarified that high-purity neon and high-purity helium can be produced at the same time, and the present invention was reached.
【００１３】すなわちこの発明は、空気分離装置の下部
精留塔上部からの放出ガス、すなわちネオン、ヘリウ
ム、水素を含む窒素ガスから凝縮分離操作で大部分の窒
素を除去する工程と、合成ゼオライトを用いた常温圧力
変動式吸着法によって残留する窒素を除去する工程と、
活性炭を用いた−１００℃以下の低温圧力変動式吸着法
によって水素を除去してネオンとヘリウムを分離する工
程とからなることを特徴とするネオン、ヘリウムの製造
方法である。That is, according to the present invention, most of the nitrogen is removed from the gas released from the upper part of the lower rectification column of the air separation device, that is, nitrogen gas containing neon, helium, and hydrogen by a condensation separation operation, and a synthetic zeolite. A step of removing residual nitrogen by the room temperature pressure fluctuation adsorption method used,
A method for producing neon and helium, which comprises a step of removing hydrogen and separating neon and helium by a low temperature pressure fluctuation type adsorption method at -100 ° C or less using activated carbon.
【００１４】[0014]
【発明の実施の形態】以下に図１に基づいてこの発明方
法を詳細に説明する。図１はこの発明のネオン、ヘリウ
ムの製造方法の系統図である。図１において、１は上塔
２と下塔３からなる空気分離装置の精留塔、４は精留塔
１の下塔３の上部より（ネオン＋ヘリウム）０．５％程
度、水素０．０５％程度、残部窒素ガスからなる放出ガ
スを原料ガスとして切替弁５、管６を介して導入される
ネオン濃縮塔である。７は分縮操作に必要な液体窒素を
ネオン濃縮塔４下部から流量調整弁８を介して供給する
液体窒素供給管で、一部不足する液体窒素は、下塔３か
ら流量調整弁９を介して供給される。１０はネオン濃縮
塔４で原料ガスと熱交換して発生する液体窒素の気化ガ
スを寒冷回収の視点から空気液化分離装置に回収する窒
素ガス回収管である。この結果、ネオン濃縮塔４の頂部
から（ネオン＋ヘリウム）６０％、水素５％、窒素３５
％程度の濃縮ガスが得られる。BEST MODE FOR CARRYING OUT THE INVENTION The method of the present invention will be described in detail below with reference to FIG. FIG. 1 is a system diagram of the method for producing neon and helium according to the present invention. In FIG. 1, 1 is a rectification column of an air separation device consisting of an upper column 2 and a lower column 3, and 4 is about 0.5% (neon + helium) from the upper part of the lower column 3 of the rectification column 1, and hydrogen is 0. It is a neon concentrating tower which is introduced through a switching valve 5 and a pipe 6 with a release gas consisting of about 05% balance nitrogen gas as a raw material gas. Reference numeral 7 is a liquid nitrogen supply pipe for supplying liquid nitrogen necessary for the decondensation operation from the lower part of the neon concentrating tower 4 through a flow rate adjusting valve 8. A part of the liquid nitrogen which is insufficient is supplied from the lower tower 3 through a flow rate adjusting valve 9. Supplied. Reference numeral 10 denotes a nitrogen gas recovery pipe for recovering the vaporized gas of liquid nitrogen generated by heat exchange with the raw material gas in the neon concentrating tower 4 to the air liquefaction separation device from the viewpoint of cold recovery. As a result, from the top of the neon concentrating tower 4 (neon + helium) 60%, hydrogen 5%, nitrogen 35
% Concentrated gas can be obtained.
【００１５】１１ａ〜１１ｃは３塔切替方式の合成ゼオ
ライトを吸着材とする窒素除去塔で、吸着、回収・再
生、昇圧工程で操業する。上記の濃縮ガスは、管１２に
より導入され、ＰＳＡ法により濃縮ガス中の窒素を吸着
除去する。１３ａ〜１３ｃは窒素除去塔１１ａ〜１１ｃ
へ濃縮ガスを導入するための切替弁である。１４ａ〜１
４ｃは窒素除去塔１１ａ〜１１ｃで窒素の除去されたネ
オン、ヘリウム、水素の混合ガスを導出するための切替
弁である。１５ａ〜１５ｃは窒素除去塔１１ａ〜１１ｃ
から吸着された窒素を脱着回収するための切替弁であ
る。１６ａ〜１６ｃは窒素除去塔１１ａ〜１１ｃに窒素
除去塔の出口ガスの一部を流量調整弁１７を介して導入
するための切替弁である。１８は窒素除去塔１１ａ〜１
１ｃを１０-3Ｔｏｒｒ以下まで減圧する真空ポンブで、
切替弁１９を介して接続されている。２０は切替弁２
１、２２を介して窒素除去塔１１ａ〜１１ｃの合成ゼオ
ライト再生時の５ｋｇ ｆ／ｃｍ2・Ｇから２ｋｇ ｆ
／ｃｍ2・Ｇ程度までの減圧時に生じるネオン、ヘリウ
ムリッチガスを５ｋｇ ｆ／ｃｍ2・Ｇ程度まで昇圧し
て窒素除去塔１１の入口ラインに戻す回収ガス圧縮機で
ある。Reference numerals 11a to 11c are nitrogen removal towers using a three-tower switching type synthetic zeolite as an adsorbent, and operate in adsorption, recovery / regeneration and pressurization steps. The above-mentioned concentrated gas is introduced through the pipe 12, and nitrogen in the concentrated gas is adsorbed and removed by the PSA method. 13a to 13c are nitrogen removal towers 11a to 11c
It is a switching valve for introducing concentrated gas into. 14a-1
Reference numeral 4c is a switching valve for leading out a mixed gas of neon, helium, and hydrogen from which nitrogen has been removed in the nitrogen removal towers 11a to 11c. 15a to 15c are nitrogen removal towers 11a to 11c
It is a switching valve for desorbing and recovering the nitrogen adsorbed from. Reference numerals 16a to 16c are switching valves for introducing a part of the outlet gas of the nitrogen removing tower into the nitrogen removing towers 11a to 11c via the flow rate adjusting valve 17. 18 is a nitrogen removal tower 11a-1
With a vacuum pump that decompresses 1c to 10 -3 Torr or less,
It is connected via a switching valve 19. 20 is a switching valve 2
5 to 15 kg f / cm 2 · G to 2 kg f during regeneration of the synthetic zeolite in the nitrogen removal towers 11a to 11c via
/ Cm 2 · neon occurring during decompression of up to approximately G, a recovery gas compressor helium rich gas pressurized to about 5kg f / cm 2 · G back to the inlet line of the nitrogen rejection column 11.
【００１６】２３は精留塔１の下塔３から管２４を介し
て液体窒素が冷却剤２５として充填された断熱槽、２６
は断熱槽２３で気化した窒素ガスの抜出し管である。２
７ａ〜２７ｃは断熱槽２３に浸漬された３塔切替方式の
活性炭が充填されたネオン精製塔で、吸着、パージ、ネ
オン回収・再生工程で操業する。ネオン精製塔２７ａ〜
２７ｃには、窒素除去塔１１ａ〜１１ｃで窒素の除去さ
れた混合ガスが管２８により導入される。２９ａ〜２９
ｃはネオン精製塔２７ａ〜２７ｃへ混合ガスを導入する
ための切替弁である。３０ａ〜３０ｃはネオン精製塔２
７ａ〜２７ｃでネオン、水素の除去された高純度ヘリウ
ムガスをヘリウムタンク３１に導出するための切替弁で
ある。３２ａ〜３２ｃはネオンタンク３３から高純度ネ
オンガスの一部（製品ネオンガス量の約５０％）をネオ
ン精製塔２７ａ〜２７ｃ内にパージのために導入するた
めの切替弁である。３４ａ〜３４ｃはパージに伴って生
じるネオン精製塔２７ａ〜２７ｃの出口ガスをネオン精
製塔２７の入口ラインに戻すための切替弁である。３５
ａ〜３５ｃはネオン精製塔２７ａ〜２７ｃのパージ終了
後、ネオン圧縮機３６によりネオン精製塔２７ａ〜２７
ｃ内を５ｋｇｆ／ｃｍ2・Ｇから１００Ｔｏｒｒまで減
圧し、高純度ネオンをネオンタンク３３に回収するため
の切替弁である。３７ａ〜３７ｃはネオン精製塔２７ａ
〜２７ｃ内を５ｋｇｆ／ｃｍ2・Ｇから１００Ｔｏｒｒ
まで減圧して高純度ネオンを回収したのち、ネオン精製
塔２７ａ〜２７ｃ内に吸着されている水素リッチガス
を、真空ポンプ３８によって１０-3Ｔｏｒｒ以下の高真
空に減圧して脱着させるための切替弁である。Reference numeral 23 denotes an adiabatic tank filled with liquid nitrogen as a coolant 25 from the lower tower 3 of the rectification tower 1 through a pipe 24, and 26.
Is an extraction pipe for the nitrogen gas vaporized in the heat insulation tank 23. 2
7a to 27c are neon refining towers filled with activated carbon of a three-column switching type immersed in the heat insulation tank 23, and operated in adsorption, purging and neon recovery / regeneration steps. Neon purification tower 27a-
A mixed gas from which nitrogen has been removed in the nitrogen removal towers 11a to 11c is introduced into the tube 27c through a pipe 28. 29a-29
Reference numeral c is a switching valve for introducing the mixed gas into the neon purification towers 27a to 27c. 30a to 30c are neon purification tower 2
It is a switching valve for leading out the high-purity helium gas from which neon and hydrogen have been removed in 7a to 27c to the helium tank 31. Reference numerals 32a to 32c are switching valves for introducing a part of high-purity neon gas (about 50% of the product neon gas amount) from the neon tank 33 into the neon purification towers 27a to 27c for purging. 34a to 34c are switching valves for returning the outlet gas of the neon purification towers 27a to 27c generated by the purge to the inlet line of the neon purification tower 27. 35
After purging the neon refining towers 27a to 27c, a to 35c are neon compressor 36 and neon refining towers 27a to 27c.
A switching valve for decompressing the inside of c from 5 kgf / cm 2 · G to 100 Torr and collecting high-purity neon in the neon tank 33. 37a to 37c are neon purification tower 27a
~ 27c from 5kgf / cm 2 · G to 100 Torr
A switching valve for decompressing the hydrogen-rich gas adsorbed in the neon purification towers 27a to 27c to a high vacuum of 10 −3 Torr or less by a vacuum pump 38 and desorbing it after decompressing to collect high-purity neon. Is.
【００１７】精留塔１の下塔の頂部から切替弁５、管６
を介して５ｋｇｆ／ｃｍ2・Ｇで抜き出されたガスは、
ネオン濃縮塔４において液体窒素供給管７および下塔３
から流量調整弁９を介して供給される大気圧の液体窒素
と熱交換して大部分の窒素が凝縮液化して除去される。
ネオン濃縮塔４で大部分の窒素が除去された（ネオン＋
ヘリウム）６０％、水素５％、窒素３５％程度の濃縮ガ
スは、５ｋｇｆ／ｃｍ2・Ｇ程度で窒素除去塔１１に導
入される。From the top of the lower tower of the rectification tower 1, a switching valve 5 and a pipe 6
The gas extracted at 5 kgf / cm 2 · G via
Liquid nitrogen supply pipe 7 and lower tower 3 in neon concentration tower 4
A large amount of nitrogen is condensed and liquefied and removed by exchanging heat with liquid nitrogen at atmospheric pressure supplied from the through the flow rate adjusting valve 9.
Most of the nitrogen was removed in the neon concentrating tower 4 (neon +
A concentrated gas of helium (60%), hydrogen (5%) and nitrogen (35%) is introduced into the nitrogen removal tower 11 at a rate of 5 kgf / cm 2 · G.
【００１８】窒素除去塔１１は、吸着、回収・再生、昇
圧工程で操業されており、例えば、窒素除去塔１１ａ
は、吸着工程であり、切替弁１３ａ、切替弁１４ａが開
放され、切替弁１５ａ、１６ａが閉止しており、５ｋｇ
ｆ／ｃｍ2・Ｇ程度、温度常温の吸着条件で、窒素を除
去し、ネオン、ヘリウム、水素の混合ガスを得る。窒素
除去塔１１ｂは、回収・再生工程であり、切替弁１３
ｂ、１４ｂ、１６ｂを閉止し、切替弁１５ｂ、切替弁１
９を開放して真空ポンプ１８で１０-3Ｔｏｒｒ以下まで
減圧することによって、合成ゼオライトに吸着されてい
た窒素を脱着させて大気放出し、窒素除去塔１１ｂ内の
合成ゼオライトを再生する。なお、５ｋｇｆ／ｃｍ2・
Ｇから２ｋｇ ｆ／ｃｍ2・Ｇ程度までの減圧時に生じ
るネオン、ヘリウムリッチガスは、切替弁１９を閉止
し、切替弁２１、２２を開放して回収ガス圧縮機２０に
より５ｋｇｆ／ｃｍ2・Ｇに昇圧して窒素除去塔１１の
入口ライン１２に戻せば、ネオン、ヘリウムの収率向上
が期待できる。窒素除去塔１１ｃは、昇圧工程であり、
切替弁１３ｃ、１４ｃ、１５ｃを閉止して切替弁１６ｃ
を開放し、流量調整弁１７を介して窒素除去塔１１ａの
出口ガスであるネオン、ヘリウム、水素の混合ガスの一
部を導入して窒素除去塔１１ｃを吸着圧力である５ｋｇ
ｆ／ｃｍ2・Ｇ程度まで圧力を上昇させる。上記の操作
を順次繰り返すことによって得られた（ネオン＋ヘリウ
ム）９０％、水素１０％程度の混合ガスは、断熱槽２３
に浸漬されたネオン精製塔２７に導入される。The nitrogen removal tower 11 is operated in the adsorption, recovery / regeneration and pressurization processes. For example, the nitrogen removal tower 11a.
Is an adsorption process, in which the switching valves 13a and 14a are opened and the switching valves 15a and 16a are closed, and 5 kg
Nitrogen is removed under adsorption conditions of f / cm 2 · G and temperature at room temperature to obtain a mixed gas of neon, helium and hydrogen. The nitrogen removal tower 11b is a recovery / regeneration process, and the switching valve 13
b, 14b, 16b are closed, the switching valve 15b, the switching valve 1
By opening 9 and reducing the pressure to 10 −3 Torr or less by the vacuum pump 18, the nitrogen adsorbed on the synthetic zeolite is desorbed and released into the atmosphere to regenerate the synthetic zeolite in the nitrogen removing tower 11b. 5 kgf / cm 2
Neon occurring during decompression from G to about 2kg f / cm 2 · G, helium-rich gas, and closes the switching valve 19, the collected gas compressor 20 by opening the switching valves 21, 22 to 5 kgf / cm 2 · G If the pressure is increased and the pressure is returned to the inlet line 12 of the nitrogen removing tower 11, it is expected that the yields of neon and helium will be improved. The nitrogen removal tower 11c is a pressurization process,
Switching valve 13c, 14c, 15c is closed and switching valve 16c
Is opened, and a part of the mixed gas of neon, helium, and hydrogen, which is the outlet gas of the nitrogen removing tower 11a, is introduced through the flow rate adjusting valve 17 and the nitrogen removing tower 11c has an adsorption pressure of 5 kg.
Increase the pressure to about f / cm 2 · G. A mixed gas of 90% (neon + helium) and 10% hydrogen obtained by sequentially repeating the above operation was used as the adiabatic tank 23.
Is introduced into the neon refining tower 27 immersed in the.
【００１９】断熱槽２３に浸漬されたネオン精製塔２７
は、吸着、パージ、ネオン回収・再生工程で操業されて
おり、例えば、ネオン精製塔２７ａは、吸着工程であ
り、切替弁２９ａが開放し、切替弁３０ａが最初は閉止
しているが所定圧になると開放し、切替弁３２ａ、３４
ａ、３５ａ、３７ａが閉止しており、５ｋｇｆ／ｃｍ2
・Ｇ程度、温度−１９６℃の条件で、ネオン、水素を活
性炭に吸着させることによって、高純度ヘリウムを流出
させてヘリウムタンク３１に回収する。ネオン精製塔２
７ｂは、パージ工程であり、吸着工程終了後、切替弁２
９ｂ、３０ｂが閉止され、切替弁３２ｂ、３４ｂが開放
されてネオン精製塔２７ｂ内に残存するヘリウムを、ネ
オンタンク３３からの高純度ネオンガスの一部（製品ネ
オンガス量の約５０％）を用いてパージする。パージに
伴って生じる出口ガスは、切替弁３４ｂを介してネオン
精製塔２７の入口ラインの管２８に戻す。ネオン精製塔
２７ｃは、ネオン回収・再生工程であり、パージ工程終
了後、切替弁３２ｃ、３４ｃを閉止し、切替弁３５ｃを
開放してネオン圧縮機３６を起動し、ネオン精製塔２７
ｃ内を５ｋｇ ｆ／ｃｍ2・Ｇから１００Ｔｏｒｒまで
減圧し、高純度ネオンをネオンタンク３３に回収する。
さらに、高純度ネオンを回収したのち、ネオン精製塔２
７ｃには水素リッチガスが吸着されているため、切替弁
３５ｃを閉止して切替弁３７ｃを開放し、真空ポンプ３
８を起動して１０-3Ｔｏｒｒ以下の高真空に減圧して水
素を脱着させる。上記の操作を順次繰り返すことによっ
て、高純度ネオン、高純度ヘリウムを得ることができ
る。Neon refining tower 27 immersed in heat insulation tank 23
Is in the adsorption, purging, and neon recovery / regeneration processes. For example, the neon purification tower 27a is in the adsorption process, and the switching valve 29a is opened and the switching valve 30a is initially closed, but at a predetermined pressure. And the switching valves 32a, 34 are opened.
a, 35a, 37a are closed, 5kgf / cm 2
High-purity helium is caused to flow out and collected in the helium tank 31 by adsorbing neon and hydrogen on activated carbon under the conditions of about G and a temperature of -196 ° C. Neon purification tower 2
7b is a purging process, and after the adsorption process, the switching valve 2
9b and 30b are closed, the switching valves 32b and 34b are opened, and the helium remaining in the neon purification tower 27b is removed by using a part of the high-purity neon gas from the neon tank 33 (about 50% of the product neon gas amount). Purge. The outlet gas generated by purging is returned to the pipe 28 of the inlet line of the neon purification tower 27 via the switching valve 34b. The neon purification tower 27c is a neon recovery / regeneration step, and after the purging step is completed, the switching valves 32c and 34c are closed, the switching valve 35c is opened, and the neon compressor 36 is started to start the neon purification tower 27.
The inside of c is depressurized from 5 kg f / cm 2 · G to 100 Torr, and high-purity neon is collected in the neon tank 33.
Furthermore, after recovering high-purity neon, the neon purification tower 2
Since hydrogen-rich gas is adsorbed on 7c, the switching valve 35c is closed and the switching valve 37c is opened, and the vacuum pump 3
8 is started to reduce the pressure to a high vacuum of 10 −3 Torr or less to desorb hydrogen. High-purity neon and high-purity helium can be obtained by sequentially repeating the above operation.
【００２０】図２は前記図１のプロセスを簡素化する目
的で、窒素除去塔１１およびネオン精製塔２７を１塔式
としてバッチ操業を行うよう改善したもので、図１と同
じ装置ならびに部材は同じ符号を付してある。図２にお
いて、ネオン濃縮塔４の頂部から（ネオン＋ヘリウム）
６０％、水素５％、窒素３５％程度の濃縮ガスが得られ
る工程は、図１と同一である。In order to simplify the process of FIG. 1, FIG. 2 is an improvement in that the nitrogen removal tower 11 and the neon purification tower 27 are of a single-column type for batch operation. The same apparatus and members as in FIG. The same reference numerals are attached. In FIG. 2, from the top of the neon concentration tower 4 (neon + helium)
The process of obtaining a concentrated gas of about 60%, 5% hydrogen, and 35% nitrogen is the same as in FIG.
【００２１】４１はネオン濃縮塔４の頂部からの（ネオ
ン＋ヘリウム）６０％、水素５％、窒素３５％程度の濃
縮ガスを貯蔵する目的で圧縮する濃縮ガス圧縮機、４２
は濃縮ガス圧縮機４１で圧縮された濃縮ガスを貯蔵する
濃縮ガスタンク、１１は合成ゼオライトを吸着材として
充填した窒素除去塔で、濃縮ガスタンク４２から管４３
を介して濃縮ガスが供給され、ＰＳＡ法により濃縮ガス
中の窒素を吸着除去する。１３は窒素除去塔１１へ濃縮
ガスを導入するための切替弁である。４４は窒素除去塔
１１で窒素の除去されたネオン、ヘリウム、水素の混合
ガスを導出するための圧力調整弁である。１８は窒素除
去塔１１を１０-3Ｔｏｒｒ以下まで減圧する真空ポンブ
で、切替弁１９を介して接続されている。４５は昇圧時
に窒素除去塔１１に後述するネオン精製塔のパージ工程
での出口ガスの一部をバッファタンク４６から導入する
ための切替弁である。２１は窒素除去塔１１の合成ゼオ
ライト再生時の５ ｋｇｆ／ｃｍ2・Ｇから２ ｋｇｆ
／ｃｍ2・Ｇ程度までの減圧時に生じるネオン、ヘリウ
ムリッチガスを濃縮ガス圧縮機４１の入口ラインに戻す
切替弁である。Reference numeral 41 designates a concentrated gas compressor for compressing for the purpose of storing a concentrated gas of about 60% (neon + helium), 5% hydrogen and 35% nitrogen from the top of the neon concentrating tower 4, 42
Is a concentrated gas tank for storing the concentrated gas compressed by the concentrated gas compressor 41, 11 is a nitrogen removal tower filled with synthetic zeolite as an adsorbent, and is a pipe 43 from the concentrated gas tank 42.
The concentrated gas is supplied through the column and the nitrogen in the concentrated gas is adsorbed and removed by the PSA method. Reference numeral 13 is a switching valve for introducing the concentrated gas into the nitrogen removing tower 11. Reference numeral 44 is a pressure control valve for leading out a mixed gas of neon, helium, and hydrogen from which nitrogen has been removed in the nitrogen removal tower 11. Reference numeral 18 denotes a vacuum pump for reducing the pressure of the nitrogen removal tower 11 to 10 -3 Torr or less, which is connected via a switching valve 19. Reference numeral 45 is a switching valve for introducing a part of the outlet gas from the buffer tank 46 into the nitrogen removal tower 11 at the time of pressurization in the purging step of the neon purification tower described later. 21 is 5 kgf / cm 2 · G to 2 kgf when regenerating the synthetic zeolite in the nitrogen removal tower 11.
A switching valve for returning the neon and helium rich gas generated when the pressure is reduced to about / cm 2 · G to the inlet line of the concentrated gas compressor 41.
【００２２】２３は精留塔１の下塔３から管２４を介し
て液体窒素が冷却剤２５として充填された断熱槽、２６
は断熱槽２３で気化した窒素ガスの抜出し管である。２
７は断熱槽２３に浸漬された活性炭が充填されたネオン
精製塔で、吸着、パージ、ネオン回収・再生工程の順に
運転する。ネオン精製塔２７には、窒素除去塔１１で窒
素の除去された混合ガスが管２８により導入される。２
９はネオン精製塔２７へ混合ガスを導入するための切替
弁である。４７はネオン精製塔２７からの高純度ヘリウ
ムを切替弁４８を介してヘリウムタンク３１へ回収する
と共に、ネオン精製塔２７のパージガスを切替弁４９を
介してバッファタンク４６に導出するための圧力調整弁
である。３２はネオンタンク３３から高純度ネオンガス
の一部（製品ネオンガス量の約５０％）をネオン精製塔
２７内にパージのために導入するための切替弁である。
３５はネオン精製塔２７のパージ終了後、ネオン圧縮機
３６によりネオン精製塔２７内を５ｋｇ ｆ／ｃｍ2・
Ｇから１００Ｔｏｒｒまで減圧し、高純度ネオンをネオ
ンタンク３３に回収するための切替弁である。３７はネ
オン精製塔２７内をネオン圧縮機３６により５ｋｇ ｆ
／ｃｍ2・Ｇから１００Ｔｏｒｒまで減圧して高純度ネ
オンを回収したのち、ネオン精製塔２７内に吸着されて
いる水素リッチガスを前記真空ポンプ１８によって１０
-3Ｔｏｒｒ以下の高真空に減圧して水素を脱着させるた
めの切替弁である。Reference numeral 23 is an adiabatic tank filled with liquid nitrogen as a coolant 25 from the lower tower 3 of the rectification tower 1 through a pipe 24, 26
Is an extraction pipe for the nitrogen gas vaporized in the heat insulation tank 23. 2
Reference numeral 7 is a neon refining tower filled with activated carbon immersed in the heat insulation tank 23, which is operated in the order of adsorption, purging, and neon recovery / regeneration steps. A mixed gas from which nitrogen has been removed by the nitrogen removal tower 11 is introduced into the neon purification tower 27 through a pipe 28. 2
Reference numeral 9 is a switching valve for introducing the mixed gas into the neon purification tower 27. Reference numeral 47 is a pressure adjusting valve for recovering the high-purity helium from the neon purification tower 27 into the helium tank 31 via the switching valve 48 and discharging the purge gas of the neon purification tower 27 to the buffer tank 46 via the switching valve 49. Is. Reference numeral 32 is a switching valve for introducing a part of the high-purity neon gas (about 50% of the product neon gas amount) from the neon tank 33 into the neon purification tower 27 for purging.
After the purging of the neon purification tower 27, 35 is 5 kg f / cm 2 · in the neon purification tower 27 by the neon compressor 36.
A switching valve for reducing the pressure from G to 100 Torr and collecting high-purity neon in the neon tank 33. 37 is 5 kg f in the neon purification tower 27 by the neon compressor 36.
High-purity neon is recovered by reducing the pressure from / cm 2 · G to 100 Torr, and the hydrogen-rich gas adsorbed in the neon purification tower 27 is removed by the vacuum pump 18 to 10
A switching valve for desorbing hydrogen by reducing the pressure to a high vacuum of -3 Torr or less.
【００２３】精留塔１の下塔３の頂部から切替弁５、管
６を介して５ｋｇ ｆ／ｃｍ2・Ｇで抜き出された放出
ガスは、図１と同様にネオン濃縮塔４において大部分の
窒素が凝縮液化して除去される。ネオン濃縮塔４で大部
分の窒素が除去された（ネオン＋ヘリウム）６０％、水
素５％、窒素３５％程度の濃縮ガスは、濃縮ガス圧縮機
４１で昇圧されたのち、濃縮ガスタンク４２で一時貯蔵
される。The discharged gas extracted from the top of the lower tower 3 of the rectification tower 1 through the switching valve 5 and the pipe 6 at 5 kgf / cm 2 · G is large in the neon enrichment tower 4 as in FIG. Part of the nitrogen is condensed and liquefied and removed. Most of the nitrogen was removed in the neon concentrating tower 4 (neon + helium) 60%, hydrogen 5%, and nitrogen 35% concentrated gas was pressurized in the concentrated gas compressor 41 and then temporarily stored in the concentrated gas tank 42. Stored.
【００２４】窒素除去塔１１は、吸着、回収・再生、昇
圧工程の順に運転されており、吸着工程では、切替弁１
３が開放され、切替弁１９、２１、４５が閉止してい
る。濃縮ガスタンク４２から管４３を経由して導入され
た濃縮ガスは、圧力調整弁４４により５ｋｇ ｆ／ｃｍ
2・Ｇ程度、温度常温の吸着条件で、窒素を除去し、
（ネオン＋ヘリウム）９０％、水素１０％程度の混合ガ
スとなって、圧力調整弁４４、切替弁２９を介して断熱
槽２３に浸漬されたネオン精製塔２７に導入される。回
収・再生工程では、切替弁１３、２１、２９、４５を閉
止し、切替弁１９を開放して真空ポンプ１８で１０-3Ｔ
ｏｒｒ以下まで減圧することによって、合成ゼオライト
に吸着されていた窒素を脱着させて回収し、窒素除去塔
１１内の合成ゼオライトを再生する。なお、５ｋｇ ｆ
／ｃｍ2・Ｇから２ｋｇ ｆ／ｃｍ2・Ｇ程度までの減圧
時に生じるネオン、ヘリウムリッチガスは、切替弁１９
を閉止し、切替弁２１を開放して濃縮ガス圧縮機４１に
より昇圧して濃縮ガスタンク４２に戻せば、ネオン、ヘ
リウムの収率向上が期待できる。昇圧工程では、切替弁
１３、１９、２１、２９を閉止して切替弁４５を開放
し、バッファタンク４６に貯蔵されたネオン精製塔２７
のパージガスを導入して窒素除去塔１１を吸着圧力であ
る５ｋｇ ｆ／ｃｍ2・Ｇ程度まで圧力を上昇させる操
作が順次繰り返される。The nitrogen removal tower 11 is operated in the order of adsorption, recovery / regeneration and pressurization process. In the adsorption process, the switching valve 1 is operated.
3 is open and the switching valves 19, 21, 45 are closed. The concentrated gas introduced from the concentrated gas tank 42 through the pipe 43 is 5 kg f / cm by the pressure adjusting valve 44.
Nitrogen is removed under adsorption conditions of about 2 G and temperature at room temperature.
A mixed gas of (neon + helium) 90% and hydrogen 10% is introduced into the neon purification tower 27 immersed in the heat insulation tank 23 through the pressure regulating valve 44 and the switching valve 29. In the recovery / regeneration process, the switching valves 13, 21, 29, 45 are closed, the switching valve 19 is opened, and the vacuum pump 18 operates at 10 −3 T.
By reducing the pressure to or below, the nitrogen adsorbed on the synthetic zeolite is desorbed and recovered, and the synthetic zeolite in the nitrogen removing tower 11 is regenerated. 5 kg f
/ Cm 2 · neon occurring during decompression from G to about 2kg f / cm 2 · G, helium-rich gas switching valve 19
If the valve is closed, the switching valve 21 is opened, the pressure is increased by the concentrated gas compressor 41, and the pressure is returned to the concentrated gas tank 42, the yields of neon and helium can be improved. In the pressurization process, the switching valves 13, 19, 21, 29 are closed and the switching valve 45 is opened, and the neon purification tower 27 stored in the buffer tank 46 is stored.
The operation of introducing the purging gas and increasing the pressure of the nitrogen removing tower 11 to the adsorption pressure of about 5 kgf / cm 2 · G is sequentially repeated.
【００２５】断熱槽２３に浸漬されたネオン精製塔２７
は、吸着、パージ、ネオン回収・再生工程の順で運転さ
れている。吸着工程では、切替弁２９が開放し、切替弁
３２、３５、３７、４９が閉止しており、導入された混
合ガスは、圧力調整弁４７により５ｋｇ ｆ／ｃｍ2・
Ｇ程度、温度−１９６℃の条件で、ネオン、水素を活性
炭に吸着させることによって、高純度ヘリウムを切替弁
４８を介してヘリウムタンク３１に回収する。パージ工
程では、吸着工程終了後、切替弁２９、４８が閉止さ
れ、切替弁３２、４９が開放されてネオン精製塔２７内
に残存するヘリウムを、ネオンタンク３３からの高純度
ネオンガスの一部（製品ネオンガス量の約５０％）を用
いてパージする。パージに伴って生じる出口ガスは、圧
力調整弁４７、切替弁４９を介してバッファタンク４６
に貯蔵される。ネオン回収・再生工程では、パージ工程
終了後、切替弁３２、４９を閉止し、切替弁３５を開放
してネオン圧縮機３６を起動し、ネオン精製塔２７内を
５ｋｇ ｆ／ｃｍ2・Ｇから１００Ｔｏｒｒまで減圧し
て脱着し、高純度ネオンをネオンタンク３３に回収す
る。さらに、高純度ネオンを回収したのち、ネオン精製
塔２７には水素リッチガスが吸着されているため、切替
弁３５を閉止して切替弁３７を開放し、真空ポンプ１８
を起動して１０-3Ｔｏｒｒ以下の高真空に減圧して水素
を脱着させて活性炭を再生する。上記の操作を順次繰り
返すことによって、高純度ネオン、高純度ヘリウムを得
ることができる。Neon refining tower 27 immersed in heat insulation tank 23
Is operated in the order of adsorption, purging, and neon recovery / regeneration processes. In the adsorption step, the switching valve 29 is opened and the switching valves 32, 35, 37, 49 are closed, and the introduced mixed gas is adjusted to 5 kg f / cm 2 · by the pressure adjusting valve 47.
High-purity helium is recovered in the helium tank 31 through the switching valve 48 by adsorbing neon and hydrogen on the activated carbon under the conditions of about G and a temperature of -196 ° C. In the purging process, after the adsorption process is completed, the switching valves 29, 48 are closed, the switching valves 32, 49 are opened, and the helium remaining in the neon purification tower 27 is partially removed from the high-purity neon gas from the neon tank 33 ( Purge with about 50% of product neon gas). The outlet gas generated by the purging is passed through the pressure adjusting valve 47 and the switching valve 49 to the buffer tank 46.
Stored in In the neon recovery / regeneration process, after the completion of the purging process, the switching valves 32 and 49 are closed, the switching valve 35 is opened, the neon compressor 36 is started, and the inside of the neon purification tower 27 is changed from 5 kg f / cm 2 · G. The pressure is reduced to 100 Torr and desorption is performed, and high-purity neon is collected in the neon tank 33. Further, after the high-purity neon is recovered, since the hydrogen-rich gas is adsorbed in the neon purification tower 27, the switching valve 35 is closed and the switching valve 37 is opened, and the vacuum pump 18
Is activated to reduce the pressure to a high vacuum of 10 −3 Torr or less to desorb hydrogen and regenerate the activated carbon. High-purity neon and high-purity helium can be obtained by sequentially repeating the above operation.
【００２６】なお、この発明において低温圧力変動式吸
着法のネオン精製塔２７における操作温度を−１００℃
以下としたのは、これ以上の温度ではネオンとヘリウム
を分離することが困難であったためである。また、この
操作温度の下限は、ネオンの融点以上であることは云う
までもない。In the present invention, the operating temperature in the neon purification tower 27 of the low temperature pressure fluctuation type adsorption method is -100.degree.
The reason for this is that it was difficult to separate neon and helium at temperatures above this. Needless to say, the lower limit of the operating temperature is not lower than the melting point of neon.
【００２７】[0027]
【実施例】空気分離装置の精留塔の下塔頂部から（ネオ
ン＋ヘリウム）０．５％程度、水素０．０５％、残部窒
素および痕跡量の酸素と低級炭化水素を含有する放出ガ
スを、図２に示すネオン濃縮塔４に５ｋｇｆ／ｃｍ2・
Ｇで導入し、液体窒素と熱交換させて大部分の窒素を凝
縮液化して除去し、（ネオン＋ヘリウム）６０％、水素
５％、窒素３５％程度の濃縮ガスを得た。この濃縮ガス
を濃縮ガス圧縮機４１で９ｋｇｆ／ｃｍ2・Ｇに昇圧し
て濃縮ガスタンク４２に貯蔵しておき、細孔径５〜９Å
の合成ゼオライトを吸着材とする窒素除去塔１１に導入
し、温度常温、５ｋｇｆ／ｃｍ2・Ｇの圧力下で濃縮ガ
ス中の窒素を吸着除去した。窒素除去塔１１の頂部から
の混合ガスは、窒素１５ｐｐｍ以下の（ネオン＋ヘリウ
ム）９０％、水素１０％程度であった。吸着完了後、窒
素除去塔１１を濃縮ガス圧縮機４１により５ｋｇｆ／ｃ
ｍ2・Ｇから２ｋｇｆ／ｃｍ2・Ｇに減圧してネオン、ヘ
リウムリッチガスを濃縮ガスタンク４２に戻したのち、
真空ポンプ１８で窒素除去塔１１内を１０-3Ｔｏｒｒ以
下に減圧し、吸着されていた窒素を脱着させて合成ゼオ
ライトを再生したのち、ネオン精製塔２７のパージに伴
って発生するガスをバッファタンク４６から導入して圧
力５ｋｇｆ／ｃｍ2・Ｇに昇圧した。[Examples] About 0.5% (neon + helium), 0.05% hydrogen, the balance nitrogen and the released gas containing trace amounts of oxygen and lower hydrocarbons were introduced from the top of the bottom of the rectification column of the air separation device. , 5 kgf / cm 2 · in the neon concentration tower 4 shown in FIG.
Introduced in G, it was heat-exchanged with liquid nitrogen to condense and liquefy most of the nitrogen, and removed (neon + helium) 60%, hydrogen 5%, and nitrogen 35% concentrated gas. This concentrated gas is pressurized to 9 kgf / cm 2 · G by the concentrated gas compressor 41 and stored in the concentrated gas tank 42, and the pore diameter is 5 to 9Å.
The synthetic zeolite of No. 1 was introduced into the nitrogen removal tower 11 using the adsorbent, and the nitrogen in the concentrated gas was adsorbed and removed at room temperature and a pressure of 5 kgf / cm 2 · G. The mixed gas from the top of the nitrogen removal tower 11 was 90% (neon + helium) of nitrogen of 15 ppm or less and about 10% of hydrogen. After the adsorption is completed, the nitrogen removal tower 11 is moved to 5 kgf / c by the concentrated gas compressor 41.
After reducing the pressure from m 2 · G to 2 kgf / cm 2 · G and returning the neon and helium rich gas to the concentrated gas tank 42,
After depressurizing the inside of the nitrogen removing tower 11 to 10 −3 Torr or less by the vacuum pump 18 to desorb the adsorbed nitrogen and regenerate the synthetic zeolite, the gas generated by purging the neon purifying tower 27 is generated in the buffer tank. It was introduced from 46 and the pressure was increased to 5 kgf / cm 2 · G.
【００２８】窒素除去塔１１からの窒素１５ｐｐｍ以下
の（ネオン＋ヘリウム）９０％、水素１０％程度の混合
ガスは、液体窒素を冷却剤２５として充填した断熱槽２
３に浸漬された活性炭を吸着材とするネオン精製塔２７
に導入し、圧力５ｋｇｆ／ｃｍ2・Ｇ、温度−１９６℃
の条件で混合ガスからネオン、水素を吸着させて、吸着
されずに流出するヘリウムをヘリウムタンク３１に純度
９９．９９９％以上で回収した。吸着終了後、ネオン精
製塔２７内に残存するヘリウムを高純度ネオンガスの一
部（製品ネオンガス量の約５０％）を用いてパージして
パージガスをバッファタンク４６に回収したのち、ネオ
ン圧縮機３６を起動し、ネオン精製塔２７内を５ｋｇｆ
／ｃｍ2・Ｇから１００Ｔｏｒｒまで減圧して脱着さ
せ、純度９９．９９５％以上のネオンをネオンタンク３
３に回収した。ネオン回収後、真空ポンプ１８によりネ
オン精製塔２７内を１０-3Ｔｏｒｒ以下に減圧して水素
リッチガスを脱着させて吸着剤を再生した。A mixed gas containing 15% or less of nitrogen (neon + helium) of 90% and hydrogen of about 10% from the nitrogen removing tower 11 is a heat insulating tank 2 filled with liquid nitrogen as a coolant 25.
Neon purification tower 27 using activated carbon immersed in No. 3 as adsorbent
Introduced into, pressure 5kgf / cm 2 · G, temperature -196 ° C
Neon and hydrogen were adsorbed from the mixed gas under the condition of No. 2, and the helium flowing out without being adsorbed was recovered in the helium tank 31 with a purity of 99.999% or more. After the adsorption is completed, the helium remaining in the neon purification tower 27 is purged by using a part of the high-purity neon gas (about 50% of the product neon gas amount) to collect the purge gas in the buffer tank 46, and then the neon compressor 36 is set. Start up, 5kgf in the neon purification tower 27
/ Cm 2 · G to 100 Torr by depressurizing and desorbing neon with a purity of 99.995% or more neon tank 3
Recovered to 3. After the neon was collected, the inside of the neon purification tower 27 was depressurized to 10 −3 Torr or less by the vacuum pump 18 to desorb the hydrogen-rich gas and regenerate the adsorbent.
【００２９】[0029]
【発明の効果】以上述べたとおり、この発明方法によれ
ば、空気分離装置の下部精留塔上部からの放出ガスを原
料として、安価に高純度のネオンおよびヘリウムを製造
することができる。As described above, according to the method of the present invention, high-purity neon and helium can be produced inexpensively using the gas released from the upper part of the lower rectification column of the air separation device as a raw material.
【図１】この発明の連続方式のネオン、ヘリウムの製造
方法の系統図である。FIG. 1 is a system diagram of a method for producing continuous neon and helium according to the present invention.
【図２】この発明のバッチ方式のネオン、ヘリウムの製
造方法の系統図である。FIG. 2 is a system diagram of a batch-type method for producing neon and helium according to the present invention.
１ 精留塔 ２ 上塔 ３ 下塔 ４ ネオン濃縮塔 ５、１３ａ〜１３ｃ、１４ａ〜１４ｃ、１５ａ〜１５
ｃ、１６ａ〜１６ｃ、１９、２１、２２ 切替弁 ６、１２、２４、２８、４３ 管 ７ 液体窒素供給管 ８、９、１７ 流量調整弁 １０ 窒素ガス回収管 １１、１１ａ〜１１ｃ 窒素除去塔 １８、３８ 真空ポンプ ２０ 回収ガス圧縮機 ２３ 断熱槽 ２５ 冷却剤 ２６ 抜出し管 ２７、２７ａ〜２７ｃ ネオン精製塔 ２９ａ〜２９ｃ、３０ａ〜３０ｃ、３２ａ〜３２ｃ、３
４ａ〜３４ｃ、３５ａ〜３５ｃ、３７ａ〜３７ｃ 切替
弁 ３１ ヘリウムタンク ３３ ネオンタンク ３６ ネオン圧縮機 ４１ 濃縮ガス圧縮機 ４２ 濃縮ガスタンク １３、２９、３２、３５、３７、４５、４８、４９ 切
替弁 ４４、４７ 圧力調整弁 ４６ バッファタンク1 Fractionation tower 2 Upper tower 3 Lower tower 4 Neon concentration tower 5, 13a-13c, 14a-14c, 15a-15
c, 16a to 16c, 19, 21, 22 Switching valve 6, 12, 24, 28, 43 pipe 7 Liquid nitrogen supply pipe 8, 9, 17 Flow rate adjusting valve 10 Nitrogen gas recovery pipe 11, 11a to 11c Nitrogen removal tower 18 , 38 Vacuum pump 20 Collected gas compressor 23 Insulation tank 25 Coolant 26 Extraction pipe 27, 27a to 27c Neon purification tower 29a to 29c, 30a to 30c, 32a to 32c, 3
4a-34c, 35a-35c, 37a-37c Switching valve 31 Helium tank 33 Neon tank 36 Neon compressor 41 Concentrated gas compressor 42 Concentrated gas tank 13, 29, 32, 35, 37, 45, 48, 49 Switching valve 44, 47 Pressure regulating valve 46 Buffer tank
Claims (1)
出ガス、すなわちネオン、ヘリウム、水素を含む窒素ガ
スから凝縮分離操作で大部分の窒素を除去する工程と、
合成ゼオライトを用いた常温圧力変動式吸着法によって
残留する窒素を除去する工程と、活性炭を用いた−１０
０℃以下の低温圧力変動式吸着法によって水素を除去し
てネオンとヘリウムを分離する工程とからなることを特
徴とするネオン、ヘリウムの製造方法。1. A step of removing most of nitrogen from a gas discharged from the upper part of a lower rectification column of an air separation device, that is, a nitrogen gas containing neon, helium, and hydrogen by a condensation separation operation,
A step of removing residual nitrogen by a room temperature pressure swing adsorption method using synthetic zeolite, and -10 using activated carbon.
A process for producing neon and helium, which comprises a step of removing hydrogen and separating neon and helium by a low temperature pressure fluctuation adsorption method at 0 ° C. or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28660695A JP3268177B2 (en) | 1995-10-06 | 1995-10-06 | Method for producing neon and helium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28660695A JP3268177B2 (en) | 1995-10-06 | 1995-10-06 | Method for producing neon and helium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09110406A true JPH09110406A (en) | 1997-04-28 |
| JP3268177B2 JP3268177B2 (en) | 2002-03-25 |
Family
ID=17706597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28660695A Expired - Fee Related JP3268177B2 (en) | 1995-10-06 | 1995-10-06 | Method for producing neon and helium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3268177B2 (en) |
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| KR100869518B1 (en) * | 2005-02-11 | 2008-11-19 | 조건환 | Cryogenic Purification Method and Apparatus of Helium Gas |
| KR100873376B1 (en) * | 2006-09-19 | 2008-12-10 | 조건환 | Concentration device for neon and / or helium gas |
| EP2322888A1 (en) * | 2009-11-13 | 2011-05-18 | Linde Aktiengesellschaft | Method and device for generating a helium-neon concentrate from air |
| CN103423968A (en) * | 2013-08-01 | 2013-12-04 | 俄罗斯深冷机械制造股份公司 | System and technology of neon and helium separation and extraction |
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| KR101954809B1 (en) * | 2018-04-30 | 2019-06-11 | 티이엠씨 주식회사 | A method and an apparatus for recovering high purity Ne from gas mixture |
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|---|---|---|---|---|
| KR100869518B1 (en) * | 2005-02-11 | 2008-11-19 | 조건환 | Cryogenic Purification Method and Apparatus of Helium Gas |
| KR100873376B1 (en) * | 2006-09-19 | 2008-12-10 | 조건환 | Concentration device for neon and / or helium gas |
| EP2322888A1 (en) * | 2009-11-13 | 2011-05-18 | Linde Aktiengesellschaft | Method and device for generating a helium-neon concentrate from air |
| CN103423968B (en) * | 2013-08-01 | 2016-05-18 | 俄罗斯深冷机械制造股份公司 | A kind of neon helium separation and Extraction system and technique |
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| CN104990366B (en) * | 2015-06-16 | 2017-11-14 | 浙江新锐空分设备有限公司 | A kind of method that thick neon helium product is extracted in the liquid nitrogen from air separation unit |
| CN104990366A (en) * | 2015-06-16 | 2015-10-21 | 浙江新锐空分设备有限公司 | Method for extracting product with coarse neon and helium from liquid nitrogen of air separation plant |
| JP2021515169A (en) * | 2018-03-02 | 2021-06-17 | リンデ ゲゼルシャフト ミット ベシュレンクテル ハフツングＬｉｎｄｅ ＧｍｂＨ | Cooling system |
| KR101954809B1 (en) * | 2018-04-30 | 2019-06-11 | 티이엠씨 주식회사 | A method and an apparatus for recovering high purity Ne from gas mixture |
| KR20240039800A (en) * | 2022-09-20 | 2024-03-27 | 주식회사 패리티 | Neon-Helium Mixed Gas Component Separation System |
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| CN115676786A (en) * | 2022-10-27 | 2023-02-03 | 江苏中科敬远节能科技有限公司 | Helium-neon separation process based on silver molecular sieve adsorption at normal temperature |
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