JP3304383B2 - Hydrogen mixed gas adsorbent - Google Patents
Hydrogen mixed gas adsorbentInfo
- Publication number
- JP3304383B2 JP3304383B2 JP05676092A JP5676092A JP3304383B2 JP 3304383 B2 JP3304383 B2 JP 3304383B2 JP 05676092 A JP05676092 A JP 05676092A JP 5676092 A JP5676092 A JP 5676092A JP 3304383 B2 JP3304383 B2 JP 3304383B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- mixed gas
- synthetic zeolite
- adsorption
- hydrogen mixed
- 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
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Separation Of Gases By Adsorption (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、水素混合ガスの吸着剤
に関する。更に詳しくは、選択吸着性にすぐれた水素混
合ガスの吸着剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to an adsorbent for hydrogen gas mixtures . In more detail, we recommend hydrogen-mixed
It relates to adsorbents for combined gas .
【0002】[0002]
【従来の技術】現在、石油などの化石燃料が主たるエネ
ルギー源として用いられているが、近年これの燃焼に伴
う大気汚染、酸性雨、地球の温暖化などが問題となって
きている。こうした環境問題を解決するためにも、クリ
ーンなエネルギーの開発を急ぐ必要があり、その一つと
して水素ガスが注目されている。2. Description of the Related Art At present, fossil fuels such as petroleum are mainly used as energy sources, but in recent years, problems such as air pollution, acid rain, and global warming associated with the combustion of these fuels have arisen. In order to solve such environmental problems, it is necessary to hasten the development of clean energy, and hydrogen gas is attracting attention as one of them.
【0003】水素ガスの製造法としては、天然ガスの水
蒸気改質、メタノールの水蒸気改質、石炭ガス化などの
方法があるが、いずれも生成ガスは水素、二酸化炭素お
よびキャリヤガスとして用いられた窒素などの混合ガス
であり、純水素ガスを得るにはそれの分離操作を必要と
している。Methods for producing hydrogen gas include steam reforming of natural gas, steam reforming of methanol, and coal gasification. It is a mixed gas such as nitrogen, and it needs to be separated to obtain pure hydrogen gas.
【0004】このような水素混合ガスからの水素ガスの
分離法としては、深冷分離法、吸収法、吸着分離法、膜
分離法などがあるが、最近では吸着分離法の一つである
PSA(Presure Swing Adsorption) による分離法が注目さ
れている。このPSAによる分離法では、モレキュラシー
ブ5A(UCC社製品)が水素ガス分離用の吸着剤として用い
られている。[0004] Methods for separating hydrogen gas from such a hydrogen mixed gas include cryogenic separation, absorption, adsorption separation, membrane separation and the like.
A separation method using PSA (Presure Swing Adsorption) is attracting attention. In this PSA separation method, Molecular Sieve 5A (product of UCC) is used as an adsorbent for hydrogen gas separation.
【0005】水素混合ガスから水素ガスを分離するとい
うことは、逆に水素混合ガスから二酸化炭素ガスと窒素
ガスを吸着除去すればよいということにも通じ、モレキ
ュラシーブ5Aを吸着剤とするPSAによる分離法において
も、このような考え方に立っている。従って、PSAによ
る分離効率を高めるためには、吸着剤の選択吸着性を向
上させる必要がある。[0005] Separating hydrogen gas from a hydrogen mixed gas also means that carbon dioxide gas and nitrogen gas should be adsorbed and removed from the hydrogen mixed gas. The law also follows this line of thinking. Therefore, in order to increase the separation efficiency by PSA, it is necessary to improve the selective adsorption of the adsorbent.
【0006】[0006]
【発明が解決しようとする課題】本発明の目的は、水
素、二酸化炭素および窒素などの混合ガスに適用したと
き、選択吸着性を向上させた吸着剤となり得る水素混合
ガスの吸着剤を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a hydrogen mixed gas which can be an adsorbent with improved selective adsorption when applied to a mixed gas such as hydrogen, carbon dioxide and nitrogen.
An object of the present invention is to provide a gas adsorbent .
【0007】[0007]
【課題を解決するための手段】かかる本発明の目的は、
遷移金属含有合成ゼオライトAをCaイオン交換反応させ
て得られたCa含有合成ゼオライトAよりなる水素混合ガ
スの吸着剤によって達成される。DISCLOSURE OF THE INVENTION The object of the present invention is to:
Hydrogen mixed gas comprising Ca-containing synthetic zeolite A obtained by Ca ion exchange reaction of transition metal-containing synthetic zeolite A
This is achieved by a gas adsorbent .
【0008】遷移金属含有合成ゼオライトAは、アルミ
ン酸ナトリウム水溶液とけい酸ナトリウム水溶液とを反
応させて合成ゼオライトAを製造するに際し、ゼオライ
トA合成母液中に遷移金属の無機塩水溶液を添加して反
応させることにより得られる。Transition metal-containing synthetic zeolite A is produced by reacting an aqueous solution of sodium aluminate and an aqueous solution of sodium silicate to produce synthetic zeolite A, in which an aqueous inorganic salt solution of a transition metal is added to the zeolite A synthetic mother liquor to cause the reaction. obtained by
【0009】アルミン酸ナトリウム水溶液とけい酸ナト
リウム水溶液(水ガラスの水溶液を含む)との反応は、従
来の反応方法に従って行われるが、その際Ni、Co、Cuな
どの遷移金属の塩化物、硝酸塩、硫酸塩などの水溶液
が、ゼオライトAの合成母液中に添加され、反応せしめ
る。The reaction of an aqueous sodium aluminate solution with an aqueous sodium silicate solution (including an aqueous solution of water glass) is carried out according to a conventional reaction method. An aqueous solution of sulfate or the like is added into the synthesis mother liquor of Zeolite A and allowed to react.
【0010】遷移金属は、酸化物換算でアルミン酸ナト
リウムに由来するAl2O3に対して約0.1〜0.4のモル比で
用いられる。これ以下では遷移金属の担持量が少なす
ぎ、一方これ以上のモル比のものは合成が困難となる。
また、Al2O3に対して、SiO2は約1.8〜2.2、好ましくは
約1.8〜2.0、H2Oは約200〜300、好ましくは約220〜250
のモル比で用いられる。The transition metal is used in a molar ratio of about 0.1-0.4 to Al 2 O 3 derived from sodium aluminate in terms of oxide. If the molar ratio is less than this, the supported amount of the transition metal is too small.
Also, relative to Al2O3 , SiO2 is about 1.8-2.2, preferably about 1.8-2.0, H2O is about 200-300, preferably about 220-250.
used in a molar ratio of
【0011】反応は、強撹拌条件下で、アルミン酸ナト
リウム水溶液にけい酸ナトリウム水溶液を瞬時に加え、
このゼオライトA合成母液中に更に遷移金属の無機塩水
溶液を加え、このようにして得られた合成母液を約30〜
60分間撹拌し、その後耐圧容器に入れ、室温〜約120℃
で約5〜60時間、好ましくは約100〜120℃で約5〜40時間
保持することによって行われる。The reaction is carried out by instantaneously adding an aqueous sodium silicate solution to an aqueous sodium aluminate solution under strong stirring conditions,
An aqueous inorganic salt solution of a transition metal is further added to this zeolite A synthetic mother liquor, and the synthetic mother liquor obtained in this way is
Stir for 60 minutes, then place in a pressure-resistant container and heat at room temperature to about 120°C.
for about 5 to 60 hours, preferably about 100 to 120°C for about 5 to 40 hours.
【0012】従来法では、ゼオライトAの合成、アンミ
ン錯体水溶液の調製およびイオン交換あるいは含浸担持
の3工程を経て遷移金属担持合成ゼオライトAを得てい
るが、上記方法では1工程で遷移金属を含有する合成ゼ
オライトAを得ることができる。In the conventional method, transition metal-supported synthetic zeolite A is obtained through three steps of synthesis of zeolite A, preparation of an aqueous ammine complex solution, and ion exchange or impregnation support. Synthetic zeolite A can be obtained.
【0013】このようにして得られた遷移金属含有合成
ゼオライトAは、約0.1〜1モル濃度のカルシウム塩水溶
液、例えば塩化カルシウム、硝酸カルシウムなどの水溶
液中に浸漬することにより、Caイオン交換反応させる。
浸漬は、室温下では約48〜60時間程度行われ、加熱する
場合には用いられた水溶液の還流温度以下で行われる。The transition metal-containing synthetic zeolite A thus obtained is immersed in an aqueous calcium salt solution having a concentration of about 0.1 to 1 mol, such as an aqueous solution of calcium chloride, calcium nitrate, etc., to cause a Ca ion exchange reaction. .
The immersion is carried out at room temperature for about 48 to 60 hours, and when heated, the temperature is below the reflux temperature of the aqueous solution used.
【0014】得られたカルシウム含有合成ゼオライトA
は、水素ガスをそれの混合ガスから分離する際の吸着剤
として有効に利用される。吸着は、種々の方法で行い得
るが、好ましくはPSA分離法によって行われる。この分
離法に用いられる装置としては、単塔式、2塔式および
それ以外の多塔式のものが挙げられる。Calcium-containing synthetic zeolite A obtained
is effectively used as an adsorbent in separating hydrogen gas from its mixture. Adsorption can be done in a variety of ways, but is preferably done by the PSA separation method. Apparatuses used in this separation method include single-column, double-column and other multi-column devices.
【0015】[0015]
【発明の効果】水素混合ガスからの水素ガスの分離に際
し、ガス吸着剤として遷移金属含有合成ゼオライトAを
Caイオン交換反応させて得られたカルシウム含有合成ゼ
オライトAを用いると、従来PSA分離法に用いられてい
るモレキュラシーブ5Aを用いた場合よりは、CO2吸着量
が若干低下するものの、N2吸着量が多く、H2-CO2-N2混
合ガスからCO2およびN2を除去する場合の指標としての
吸着量比(CO2吸着量+N2吸着量)/(H2吸着量)をとって比
較してみた場合、吸着選択性にすぐれているという効果
が奏せられる。Effects of the Invention When separating hydrogen gas from a hydrogen mixed gas, a transition metal-containing synthetic zeolite A is used as a gas adsorbent.
When using the calcium-containing synthetic zeolite A obtained by Ca ion exchange reaction , the CO 2 adsorption amount is slightly lower than when molecular sieve 5A, which is conventionally used in the PSA separation method, is used, but the N 2 adsorption amount is is large, and the adsorption amount ratio ( CO2 adsorption amount + N2 adsorption amount) / ( H2 adsorption amount) is taken as an index when removing CO2 and N2 from H2 - CO2 - N2 mixed gas. When compared, the effect of excellent adsorption selectivity can be obtained.
【0016】[0016]
【実施例】次に、実施例について本発明を説明する。EXAMPLES The present invention will now be described with reference to examples.
【0017】実施例
アルミン酸ナトリウムNa2O・Al2O3
水ガラスNa2O・nSiO2
硝酸ニッケルNi(NO3)2・6H2O
以上の3成分を水溶液として、酸化物換算で1.0 Al2O3
・1.82 SiO2・0.101 NiO・235 H2Oのモル比になるよう
に、この順序で瞬時に混合し、撹拌した。この合成母液
を耐圧容器に入れ、120℃で10時間加熱して、Ni含有合
成ゼオライトAを得た。Example Sodium aluminate Na 2 O.Al 2 O 3 Water glass Na 2 O.n SiO 2 Nickel nitrate Ni(NO 3 ) 2.6H 2 O 2O3 _
- 1.82 SiO2 - 0.101 NiO - 235 H2O , and instantaneously mixed and stirred in this order. This synthetic mother liquor was placed in a pressure vessel and heated at 120° C. for 10 hours to obtain a Ni-containing synthetic zeolite A.
【0018】得られたNi含有合成ゼオライトA20gを、1
モル濃度の塩化カルシウム水溶液200ml中に室温下で48
時間浸漬し、Caイオン交換反応(交換率約30%)を行っ
た。20 g of the resulting Ni-containing synthetic zeolite A was
48 at room temperature in 200 ml of molarity calcium chloride aqueous solution.
It was immersed for a period of time, and a Ca ion exchange reaction (exchange rate of about 30%) was performed.
【0019】このCa含有合成ゼオライトAを、673Kで5
時間熱処理した後、更に約1.5kPaの減圧下で、473Kで1
時間乾燥させ、純H2ガス、純N2ガスまたは純CO2ガスに
ついての吸着量を、吸着温度298K、吸着圧力208kPa、吸
着時間30分間の条件下で個々に測定した。そして、吸着
量は、吸着量測定装置内に組み込まれた圧力センサによ
って観測される圧力変動から算出された。This Ca-containing synthetic zeolite A was heated at 673K for 5
After heat treatment for 1 hour, further heat treatment at 473 K under a reduced pressure of about 1.5 kPa for 1
Time drying, the adsorption amount for pure H2 gas, pure N2 gas or pure CO2 gas was individually measured under the conditions of adsorption temperature 298K , adsorption pressure 208kPa, adsorption time 30min. Then, the adsorption amount was calculated from the pressure fluctuation observed by the pressure sensor incorporated in the adsorption amount measuring device.
【0020】比較例1
実施例で用いられたNi含有合成ゼオライトAについて、
実施例と同様の測定が行われた。Comparative Example 1 Regarding the Ni-containing synthetic zeolite A used in the examples,
Measurements similar to those in the examples were performed.
【0021】 比較例2
モレキュラシーブ5A(CaA型)を用いて、実施例と同様の
測定が行われた。Comparative Example 2 Using molecular sieve 5A (CaA type) , the same measurement as in Example was performed.
【0022】比較例3
モレキュラシーブ5A 20gを、1モル濃度のNiヘキサアン
ミン錯体水溶液200ml中に室温下で48時間浸漬し、Niを
分子中のNaおよびCaとイオン交換的に担持させた(イオ
ン交換率約19%)。これを用いて、実施例と同様の測定が
行われた。Comparative Example 3 20 g of molecular sieve 5A was immersed in 200 ml of a 1 mol concentration Ni hexaammine complex aqueous solution at room temperature for 48 hours to ion-exchange Ni with Na and Ca in the molecule (ion exchange rate of about 19%). Using this, the same measurements as in the example were performed.
【0023】以上の実施例および各比較例における測定
結果は、次の表に示される。
表
吸着量[/cm3(sтp)/cm3吸着剤] 吸着量比
例 H2 N2 CO2 [q(CO2)+q(N2)]/q(H2)
実施例 0.852 3.775 12.886 19.555
比較例1 0.985 3.412 13.220 16.885
〃 2 0.851 2.953 13.115 18.881
〃 3 0.934 3.057 13.218 17.425The measurement results in the above examples and comparative examples are shown in the following table. Table adsorption amount [/cm 3 (stp)/cm 3 adsorbent] adsorption amount proportional H 2 N 2 CO 2 [q(CO 2 ) + q(N 2 )]/q(H 2 ) Example 0.852 3.775 12.886 19.555 Comparative Example 1 0.985 3.412 13.220 16.885 〃 2 0.851 2.953 13.115 18.881 〃 3 0.934 3.057 13.218 17.425
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) C01B 33/00 - 39/54 B01D 53/02 B01D 53/04 B01J 20/18 CA(STN) JICSTファイル(JOIS)──────────────────────────────────────────────────── ─── Continuation of the front page (58) Researched field (Int.Cl. 7 , DB name) C01B 33/00 - 39/54 B01D 53/02 B01D 53/04 B01J 20/18 CA (STN) JICST file ( JOIS)
Claims (1)
ン交換反応させて得られたCa含有合成ゼオライトAより
なる水素混合ガスの吸着剤。[Claim 1] From Ca-containing synthetic zeolite A obtained by Ca ion exchange reaction of transition metal-containing synthetic zeolite A
Adsorbent for hydrogen mixed gas .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP05676092A JP3304383B2 (en) | 1992-02-07 | 1992-02-07 | Hydrogen mixed gas adsorbent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP05676092A JP3304383B2 (en) | 1992-02-07 | 1992-02-07 | Hydrogen mixed gas adsorbent |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05221630A JPH05221630A (en) | 1993-08-31 |
JP3304383B2 true JP3304383B2 (en) | 2002-07-22 |
Family
ID=13036457
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP05676092A Expired - Fee Related JP3304383B2 (en) | 1992-02-07 | 1992-02-07 | Hydrogen mixed gas adsorbent |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3304383B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017170380A (en) * | 2016-03-25 | 2017-09-28 | パナソニックIpマネジメント株式会社 | Carbon dioxide adsorbing material and vacuum heat insulating material, and application of the same |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01219013A (en) * | 1988-02-27 | 1989-09-01 | Satoyuki Inui | Zeolite containing copper, its production, catalyst for removing o2 from co gas, consisting of zeolite and method for removing o2 in co gas |
JP2639562B2 (en) * | 1988-05-31 | 1997-08-13 | 日本化学工業株式会社 | Zeolite adsorbent for hydrogen PSA and method for producing the same |
JPH0284957A (en) * | 1988-09-22 | 1990-03-26 | Shinagawa Nenryo Kk | Water absorptive material |
-
1992
- 1992-02-07 JP JP05676092A patent/JP3304383B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH05221630A (en) | 1993-08-31 |
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