JPH0386237A - Olefin adsorbent - Google Patents
Olefin adsorbentInfo
- Publication number
- JPH0386237A JPH0386237A JP1218601A JP21860189A JPH0386237A JP H0386237 A JPH0386237 A JP H0386237A JP 1218601 A JP1218601 A JP 1218601A JP 21860189 A JP21860189 A JP 21860189A JP H0386237 A JPH0386237 A JP H0386237A
- Authority
- JP
- Japan
- Prior art keywords
- adsorbent
- olefin
- sulfuric acid
- ethylene
- adsorption
- 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.)
- Pending
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 34
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 239000005977 Ethylene Substances 0.000 abstract description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011282 treatment Methods 0.000 abstract description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 2
- 230000000087 stabilizing effect Effects 0.000 abstract 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 abstract 2
- 230000006866 deterioration Effects 0.000 abstract 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 235000012055 fruits and vegetables Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 235000003228 Lactuca sativa Nutrition 0.000 description 1
- 101100028920 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cfp gene Proteins 0.000 description 1
- 101100062772 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) dcl-2 gene Proteins 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Storage Of Fruits Or Vegetables (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はオレフィンの吸着剤に関し、特に、果物、野菜
などの保鮮用、長期保存用のため、植物の呼吸作用から
発生するエチレン(成熟促進作用をもつホルモン)を除
去する吸着剤に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an olefin adsorbent, and in particular, it is used to preserve the freshness and long-term preservation of fruits and vegetables. This invention relates to an adsorbent that removes hormones that have an effect on the body.
キャベツ、レタスなどが大豊作の場合の出荷調整、米国
からのサクランボの輸入などの青果物の長距離輸送、桃
などの冬期提供など青果物の保護技術が問題となってお
り、温度、酸素。Problems include the adjustment of shipments when cabbage, lettuce, etc. are in abundance, the long-distance transportation of fruits and vegetables such as importing cherries from the United States, and the provision of fruits and vegetables such as peaches during the winter.
炭酸ガスの調整に合わせて脱エチレン技術が保鮮の要と
され、種々な方法が提案され、これまでにエチレンの吸
着剤として大谷石や合成ゼオライトの使用が提案されて
いる。Ethylene removal technology, along with the adjustment of carbon dioxide gas, is considered key to freshness preservation, and various methods have been proposed, and the use of Oya stone and synthetic zeolite as ethylene adsorbents has so far been proposed.
従来の天然産の大谷石やゼオライトではオレフィンの吸
着容量が小さすぎ、合成ゼオライトによるオレフィン、
特にエチレンの吸着法では水分の影響(大気中の水分が
優先的かつ強固に吸着する)を受け、エチレンの吸着除
去作用を妨害する。そのため、従来の吸着剤によるオレ
フィンの吸着除去には、吸着剤を大量に使用するか、再
三にわたる再生頻度の大な処理を必要とするという不具
合があり、また水のように優先的に吸着する場合、前辺
って吸着しているものを追い出す必要もあり、不都合で
あるという問題点があった。Conventional naturally produced Oya stone and zeolite have too small adsorption capacity for olefins, so synthetic zeolites are able to absorb olefins,
In particular, the ethylene adsorption method is affected by moisture (moisture in the atmosphere is preferentially and strongly adsorbed), which interferes with the adsorption and removal effect of ethylene. Therefore, the adsorption and removal of olefins using conventional adsorbents has the disadvantage of requiring the use of large amounts of adsorbent or the need for repeated and frequent regeneration treatments. In this case, there was a problem in that it was necessary to remove the adsorbed material from the front, which was inconvenient.
そのため、水分の共吸着によっては影響を受けず、かつ
エチレンの大容量の吸着作用をもつ吸着剤の出現がまた
れている。Therefore, an adsorbent that is not affected by the co-adsorption of water and has a large capacity adsorption effect for ethylene has appeared.
そこで本発明者らは、これに答えるべくジルコニアに塩
化パラジウムと塩化第二銅を担持してなるオレフィンの
吸着剤を提案した(昭和63年12月23日付特許出H
)
本発明は上記提案の吸着剤よりもその性能の優れたオレ
フィンの吸着剤を提供しようとするものである。In order to solve this problem, the present inventors proposed an olefin adsorbent in which palladium chloride and cupric chloride are supported on zirconia (Patent No. H
) The present invention aims to provide an olefin adsorbent that has better performance than the adsorbents proposed above.
[1課題を解決するための手段]
本発明はジルコニウム、チタニウムからなる群の一種以
上の水酸化物を硫酸で処理した後、焼成安定化した担体
に、塩化パラジウム及び塩化鋼を担持してなることを特
徴とするオレフィンIWL着剤である。[Means for Solving the Problem 1] The present invention comprises treating one or more hydroxides of the group consisting of zirconium and titanium with sulfuric acid, and then supporting palladium chloride and steel chloride on a carrier stabilized by firing. This is an olefin IWL adhesive characterized by the following.
本発明のオレフィン吸着剤は一般的に該吸着剤全重量ベ
ースで、ZrO□及び/又はTlO2: 70〜90w
t%、SO42−: 3〜10 wt%、PdCl2:
0、1〜5 wt%、CaCl2: L 〜20 wt
%よりなるものである。The olefin adsorbent of the present invention generally contains ZrO□ and/or TlO2: 70 to 90w based on the total weight of the adsorbent.
t%, SO42-: 3-10 wt%, PdCl2:
0, 1-5 wt%, CaCl2: L ~20 wt
%.
lr及び/又はTiの水酸化物を硫酸処理する際に使用
する硫酸濃度は、−数的に0.01〜lON、好ましく
は0.1〜5Nである。The sulfuric acid concentration used when treating the hydroxide of lr and/or Ti with sulfuric acid is -numerically 0.01 to 1ON, preferably 0.1 to 5N.
〔作用]
本発明のオレフィン吸着剤のオレフィンの吸着機構につ
き、エチレンを例にとって説明する。[Operation] The olefin adsorption mechanism of the olefin adsorbent of the present invention will be explained using ethylene as an example.
CH*=CH2+PdC]□+H20→ CIIa[:
HD+Pd+28C1(1)Pd+ 2CuC12→P
dCl2+2CuC1(2)2CuCI +2HCI+
A02−2CuC12+820 (3)CH2=CH
2+ ’A02 − CLCfl(l
(4)上記反応はエチレンからアセトアルデヒド
をIL威させることで実用化されていて公知の反応であ
るが、本発明のオレフィン吸着剤には超強酸(硫酸処理
された担体)が存在するため、上記反応を常温で、なお
かつ高性能で促進する。CH*=CH2+PdC]□+H20→ CIIa[:
HD+Pd+28C1(1)Pd+ 2CuC12→P
dCl2+2CuCl(2)2CuCI+2HCI+
A02-2CuC12+820 (3) CH2=CH
2+ 'A02 - CLCfl(l
(4) The above reaction is a well-known reaction that has been put to practical use by subjecting acetaldehyde from ethylene to IL reaction, but since the olefin adsorbent of the present invention contains a super strong acid (sulfuric acid treated carrier), the Accelerates reactions at room temperature and with high performance.
すなわちエチレンCH2=CLが超強酸表面のHΦと結
合して吸着するので、この反応が促進される。That is, since ethylene CH2=CL binds to and adsorbs HΦ on the surface of the super strong acid, this reaction is promoted.
また、上記反応からも判るように、水の存在は必要条件
であるので、従来の吸着剤におけるように水分の共吸着
によるオレフィンの吸着能の低下はない。アセトアルデ
ヒドが生成するが、これはアセトンなどの溶剤に可溶な
ので再生することができる。更に担体が超強酸であるの
でオレフィンの吸着容量が著しく増加する。Furthermore, as can be seen from the above reaction, since the presence of water is a necessary condition, there is no reduction in the adsorption capacity for olefins due to co-adsorption of water, unlike in conventional adsorbents. Acetaldehyde is produced, which can be recycled as it is soluble in solvents such as acetone. Furthermore, since the carrier is a superacid, the adsorption capacity for olefins is significantly increased.
固体酸の一つとして知られているHYゼオライト〔東洋
曹達工業■〕を担体とし、これに塩化銅(CuCI2)
、塩化パラジウム(PdC1,)を担持した。すなわち
、Cut: l□、 Pd[:+2を3%シュウ酸水溶
液に溶解して、担体に対しCuCL 10%、1’ d
C1□ 1%を含浸し、乾燥後300℃、3時間位J
imし、吸着試験に供した。HY zeolite (Toyo Soda Kogyo ■), which is known as a solid acid, is used as a carrier, and copper chloride (CuCI2) is added to it.
, palladium chloride (PdC1,) was supported. That is, Cut: l□, Pd[:+2 was dissolved in a 3% aqueous oxalic acid solution, and CuCL 10%, 1' d was added to the support.
C1□ Impregnated with 1% and dried at 300℃ for about 3 hours J
im and subjected to an adsorption test.
lieをキャリアーとする流通系の反応器に、上記吸着
剤を充填し、室温におけるエチレンの吸着量を計測し、
2.7 mmol/gを得た。The above adsorbent was filled in a flow system reactor using Lie as a carrier, and the amount of ethylene adsorbed at room temperature was measured.
2.7 mmol/g was obtained.
ブランクテスト (CuC1z 、 PdCLを担持し
ていないHYゼオライト担体を使用しての試験〉の結果
は、エチレンの吸着性能は0であった。The blank test (test using HY zeolite carrier not carrying CuC1z or PdCL) showed that the ethylene adsorption performance was 0.
〔実施例1〕
市販のオキシ塩化ジルコニウム(Zr[ICIz) 2
kgを純水15fに溶解させ、攪拌下で〜H、[I H
水を滴下し、pH10とし、生成した沈殿を一昼夜熟成
後、濾過洗浄、真空乾燥(100℃)して白色粉700
gを得た。この白色粉末を1モル濃度の硫酸71中に浸
漬し、硫酸担持した後に濾別し、乾燥後600℃で3時
間焼成し、超強酸とした。[Example 1] Commercially available zirconium oxychloride (Zr[ICIz) 2
kg in 15f of pure water, ~H, [I H
Water was added dropwise to adjust the pH to 10, and the resulting precipitate was aged for a day and night, filtered and washed, and vacuum dried (100°C) to give a white powder of 700%.
I got g. This white powder was immersed in 1 molar sulfuric acid 71 to support the sulfuric acid, filtered, dried, and then calcined at 600° C. for 3 hours to obtain a super strong acid.
比較例と同様に、CuCL l 0%、PdCl2 1
%を該超強酸に担持し、吸着試験に供した。Similar to the comparative example, CuCL l 0%, PdCl2 1
% was supported on the super strong acid and subjected to an adsorption test.
その結果、この吸着剤はエチレンを6.4…mol/g
吸着した。これに対し、担体の超強酸のみでは0.7
mmol/ g 、単なるZrO2にCuCI。10%
、Pd[:+21%を担持したものでは3.0 mmo
l/ gであった。As a result, this adsorbent absorbed 6.4...mol/g of ethylene.
It was absorbed. In contrast, when using only a super strong acid as a carrier, 0.7
mmol/g, CuCI in simple ZrO2. 10%
, Pd [: 3.0 mmo for the one carrying +21%
l/g.
この吸着剤がエチレンを6.4 +yunol/ g吸
着後は生成物の吸着点への被覆により失活するが、アセ
トンにより生成したC H、CHOを洗浄し、3o(]
℃で乾燥させると賦活して再生が可能である。After this adsorbent adsorbs 6.4 + yunol/g of ethylene, it is deactivated by coating the adsorption point with the product, but the generated CH and CHO are washed away with acetone, and 3o(]
It can be activated and regenerated by drying at ℃.
〔実施例2〕
実施例1のオキシ塩化ジルコニウムの代リニ四塩化チタ
ンを用いた以外は実施例1と同じ方法で吸着剤を調整し
た。[Example 2] An adsorbent was prepared in the same manner as in Example 1 except that titanium linium tetrachloride was used instead of zirconium oxychloride in Example 1.
前記した吸着試験を行った結果、この吸着剤はエチレン
を6.8 mmol/ g吸着した。As a result of the adsorption test described above, this adsorbent adsorbed 6.8 mmol/g of ethylene.
〔実施例3〕
実施例1のオキシ塩化ジルコニウムの代りに、四塩化チ
タンとオキシ塩化ジルコニウムの混合液(重量%で2r
L : T+[]□=50:50)を用いた以外は実施
例1と同じ方法で吸着剤を調整した。[Example 3] Instead of the zirconium oxychloride in Example 1, a mixed solution of titanium tetrachloride and zirconium oxychloride (2r by weight) was used.
An adsorbent was prepared in the same manner as in Example 1, except that L:T+[]□=50:50) was used.
1)g1述した吸着試験を行った結果、この吸着剤はエ
チレンを7.2 mmol/ g吸着した。1) g1 As a result of conducting the adsorption test described above, this adsorbent adsorbed 7.2 mmol/g of ethylene.
以上、本発明のオレフィンの吸着剤について、Cu C
I 2とPdCLの担持量の特定なものをあげたが、本
発明はこれに限定されるものではない。As described above, regarding the olefin adsorbent of the present invention, Cu C
Although specific supported amounts of I 2 and PdCL have been described, the present invention is not limited thereto.
また、再生法も溶剤洗浄について説明したが加熱により
生成物(CH,CHD)を除去することができるので、
実施例の手段に限定されるものではない。更に、上記実
施例では吸着剤が粉体状のものを示したが、これらを成
形して錠剤、ペレット、ハニカム状にすることもでき、
また本発明吸着剤をプラスチックス中に添加してフィル
ム状に成形して使用することもできる。In addition, the regeneration method also explained solvent cleaning, but since the products (CH, CHD) can be removed by heating,
It is not limited to the means of the embodiment. Furthermore, although the above examples show that the adsorbent is in powder form, these can also be molded into tablets, pellets, or honeycomb shapes.
The adsorbent of the present invention can also be added to plastics and formed into a film for use.
本発明吸着剤に水分の共吸着によるオレフィンの吸着が
妨げられることはなく、担体として超強酸である硫酸処
理したZrO2及び/又はTiO2を使用しているため
、オレフィンの吸着量が従来のものに比し極めて優れて
いる。The adsorption of olefins by the co-adsorption of water is not hindered by the adsorbent of the present invention, and since ZrO2 and/or TiO2 treated with sulfuric acid, which is a super strong acid, is used as a carrier, the amount of adsorption of olefins is comparable to that of conventional ones. It is extremely superior.
Claims (1)
化物を硫酸で処理した後、焼成安定化した担体に、塩化
パラジウム及び塩化銅を担持してなることを特徴とする
オレフィン吸着剤。An olefin adsorbent characterized in that palladium chloride and copper chloride are supported on a carrier that has been stabilized by firing after treating one or more hydroxides of the group consisting of zirconium and titanium with sulfuric acid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1218601A JPH0386237A (en) | 1989-08-28 | 1989-08-28 | Olefin adsorbent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1218601A JPH0386237A (en) | 1989-08-28 | 1989-08-28 | Olefin adsorbent |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0386237A true JPH0386237A (en) | 1991-04-11 |
Family
ID=16722515
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1218601A Pending JPH0386237A (en) | 1989-08-28 | 1989-08-28 | Olefin adsorbent |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0386237A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05103588A (en) * | 1991-10-14 | 1993-04-27 | Sharp Corp | Preservation equipment for vegetable-and-fruit freshness |
JPH0837920A (en) * | 1995-07-27 | 1996-02-13 | Sharp Corp | Apparatus for retaining freshness of vegetable and fruit |
US8132479B2 (en) | 2006-04-28 | 2012-03-13 | Thk Co., Ltd. | Screw device and method of manufacturing the same |
CN103097772A (en) * | 2010-09-06 | 2013-05-08 | Thk株式会社 | Rolling element screw assembly |
-
1989
- 1989-08-28 JP JP1218601A patent/JPH0386237A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05103588A (en) * | 1991-10-14 | 1993-04-27 | Sharp Corp | Preservation equipment for vegetable-and-fruit freshness |
JPH0837920A (en) * | 1995-07-27 | 1996-02-13 | Sharp Corp | Apparatus for retaining freshness of vegetable and fruit |
US8132479B2 (en) | 2006-04-28 | 2012-03-13 | Thk Co., Ltd. | Screw device and method of manufacturing the same |
CN103097772A (en) * | 2010-09-06 | 2013-05-08 | Thk株式会社 | Rolling element screw assembly |
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