JPH0424092B2 - - Google Patents
Info
- Publication number
- JPH0424092B2 JPH0424092B2 JP58034923A JP3492383A JPH0424092B2 JP H0424092 B2 JPH0424092 B2 JP H0424092B2 JP 58034923 A JP58034923 A JP 58034923A JP 3492383 A JP3492383 A JP 3492383A JP H0424092 B2 JPH0424092 B2 JP H0424092B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- organic acid
- activated carbon
- gas
- acid salts
- 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 - Lifetime
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- -1 organic acid salt Chemical class 0.000 claims description 21
- 150000002484 inorganic compounds Chemical class 0.000 claims description 15
- 229910010272 inorganic material Inorganic materials 0.000 claims description 15
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052745 lead Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 18
- 239000003463 adsorbent Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 5
- 150000004675 formic acid derivatives Chemical class 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 150000002823 nitrates Chemical class 0.000 description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910000070 arsenic hydride Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- CKMAOLFFRUZLAL-UHFFFAOYSA-N chloro(diethyl)arsane Chemical compound CC[As](Cl)CC CKMAOLFFRUZLAL-UHFFFAOYSA-N 0.000 description 1
- DXCZGVVDXIPLCQ-UHFFFAOYSA-N chloro(dimethyl)arsane Chemical compound C[As](C)Cl DXCZGVVDXIPLCQ-UHFFFAOYSA-N 0.000 description 1
- GYAOTMWLMBFNBJ-UHFFFAOYSA-N chloromethylarsane Chemical compound ClC[AsH2] GYAOTMWLMBFNBJ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- LQSFEOMOHFPNEB-UHFFFAOYSA-N dichloro(ethyl)arsane Chemical compound CC[As](Cl)Cl LQSFEOMOHFPNEB-UHFFFAOYSA-N 0.000 description 1
- FPQFKZZFKYTPNB-UHFFFAOYSA-N dichloro(propyl)arsane Chemical compound CCC[As](Cl)Cl FPQFKZZFKYTPNB-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- KQTKYCXEDDECIZ-UHFFFAOYSA-N ethylarsenic Chemical compound CC[As] KQTKYCXEDDECIZ-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- JHQSGZOIIRXESF-UHFFFAOYSA-N iodo(dimethyl)arsane Chemical compound C[As](C)I JHQSGZOIIRXESF-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- KRDDXSIKPQVLDP-UHFFFAOYSA-N methylarsenic Chemical compound [As]C KRDDXSIKPQVLDP-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Separation Of Gases By Adsorption (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
本発明はアルシン吸着剤およびアルシン含有流
体の処理方法に関する。
飲料用の炭酸ガス、コークス炉ガス、高炉ガ
ス、転炉ガス、石油留分熱分解ガス、天然ガスな
どには、アルシンが含まれており、このアルシン
は微量でも人体に極めて有害であり、また触媒毒
作用も呈するもので、飲料加工、化学反応などの
工程で問題となることが多い。
ガス中のアルシンを除去する方法として、酸化
性溶液などによる薬液洗浄法あるいは活性炭など
を用いる吸着法などが提案されているが、除去効
果が悪く、効率のよいアルシン除去方法が望まれ
ていた。
本発明者らは、このような実情に鑑み、鋭意検
討した結果、銅とアルカリ金属、アルカリ土類金
属、Al、Ti、Ｖ、Cr、Mn、Fe、Co、Ni、Zn、
Cd、Pbの金属を酸化物として含有せしめた活性
体を用いることにより、流体中のアルシンを非常
に効率よく除去できること見出し、本発明を完成
した。
すなわち、本発明は、
アルシンを含有し実質的に酸素を含有しない流
体を、銅の無機化合物または有機酸塩（以下第
一成分ということもある）と(a)アルカリ金属の
無機化合物または有機酸塩、(b)アルカリ土類金属
の無機化合物または有機酸塩および(c)Al、Ti、
Ｖ、Cr、Mn、Fe、Co、Ni、Zn、Cd、Pbの無機
化合物または有機酸塩（以下第二成分ということ
もある）の一種以上とを活性炭に添着した後130
℃以上の温度で焼成することにより上記および
の金属成分を酸化物として活性炭に含有せしめ
てなる吸着剤に接触させることを特徴とするアル
シン含有流体の処理方法、
である。
本発明において用いられる吸着剤は活性炭に前
記第一成分および第二成分を金属酸化物として含
有せしめることによつて製造することができる。
この場合に用いられる活性炭は、石炭、コーク
ス、木炭、ヤシガラ、樹脂などを原料として公知
の方法により製造されたもので、その比表面積が
200〜2000m2／ｇのものであれば、いかなるもの
でもよく、その形状はたとえば球状、円柱状、破
砕状、粉末状、繊維状などガスの処理方法に応じ
て適当なものが使用される。
本発明で用いられる銅の無機化合物としては、
たとえば炭酸塩、塩基性炭酸塩、硝酸塩、硫酸
塩、リン酸塩、ハロゲン化物、酸化物、水酸化物
などが、銅の有機酸塩としてはギ酸塩、酢酸塩、
シユウ酸塩などが挙げられる。
アルカリ金属の無機化合物としては、Li、Na、
Ｋ、Rb、Csのたとえば炭酸水素塩、炭酸塩、硝
酸塩、ホウ酸塩、ケイ酸塩、硫酸塩、ハロゲン化
物、水酸化物などが、有機酸塩としては、ギ酸
塩、酢酸塩、シユウ酸塩、安息香酸塩、フエノー
ル類の塩、スルホン酸類の塩などが挙げられる。
またアルカリ土類金属の無機化合物としては、
Be、Mg、Ca、SrおよびBaのたとえば炭酸塩、
硝酸塩、硫酸塩、リン酸塩、ハロゲン化物、酸化
物、水酸化物などが、有機酸塩としてはギ酸塩、
酢酸塩、シユウ酸塩などがあげられる。
Al、Ti、Ｖ、Cr、Mn、Fe、Co、Ni、Zn、
Cd、Pbの無機化合物としてはこれらの金属の炭
酸塩、炭酸水素塩、硝酸塩、ホウ酸塩、ケイ酸
塩、硫酸塩、リン酸塩、ハロゲン化物、水酸化
物、アンモニウム塩、酸化物などが、有機酸塩と
してはギ酸塩、酢酸塩、シユウ酸塩、安息香酸
塩、フエノール類の塩、スルホン酸類の塩などが
挙げられる。
本発明において用いられる吸着剤は活性炭に第
一成分および第二成分の双方を金属の酸化物とし
て含有せしめたものであるが、この場合、第二成
分として、アルカリ金属の無機化合物または有機
酸塩〔以下成分(a)ということもある〕単独、アル
カリ土類金属の無機化合物または有機酸塩〔以下
成分(b)ということもある〕単独またはAl、Cr、
Ti、Ｖ、Mn、Fe、Co、Ni、Zn、Cd、Pbの無機
化合物または有機酸塩〔以下成分(c)ということも
ある〕単独を用いたものであつてもよいが、これ
らのうち成分(a)と成分(b)、成分(b)と成分(c)、また
は成分(c)と成分(a)のように二種の成分を用いたも
のでもよく、成分(a)、成分(b)および成分(c)の三種
の成分を同時に含有せしめたものでもよい。また
第一成分として二種以上の化合物を用いたもので
もよく、第二成分として、たとえば成分(a)内の二
種の異なつた成分を用いるというように同種の成
分内の二種以上の異なつた成分を用いたものでも
よい。
本発明で用いる吸着剤において活性炭中の第一
成分の含量は活性炭１ｇ当り金属として0.1mg−
原子〜3.0mg−原子、好ましくは0.2mg−原子〜2.0
mg−原子であり、第二成分の含量は活性炭１ｇ当
り金属として0.1mg−原子〜5.0mg−原子、好まし
くは0.2mg−原子〜4.0mg−原子である。
活性炭に各成分を添着する方法としては、各成
分を水（酸またはアルカリ水溶液を含む）、各種
の溶媒などに溶解または懸濁させた液を活性炭に
含浸または散布し、約130℃以下の温度で、添着
活性炭中の水または溶媒を蒸発乾燥させることに
よつて行われる。焼成は130℃以上の温度で添着
活性炭を不活性ガス、炭酸ガス、水蒸気、燃焼排
ガスなどの雰囲気で加熱し、各金属の無機化合物
または有機酸塩を熱分解させることによつて行わ
れ、これにより各金属成分は酸化物として活性炭
に含有される。
本発明において流体とは気体または液体をい
い、たとえば不活性ガスまたは還元性ガスまたは
これらの液化状のものである。不活性ガスまたは
還元性ガスとしては、たとえば炭酸ガス、コーク
ス炉ガス、高炉ガス、転炉ガス、石油留分熱分解
ガス、天然ガスなどが挙げられる。
本発明の方法は、前記で得られた金属化合物含
有活性炭にアルシンを含有し実質的に酸素を含有
しない流体を接触させることにより行なわれる。
本発明における除去対象物であるアルシンはヒ素
の水素化合物およびその水素をアルキル、ハロゲ
ンで置換したものでたとえば水素化ヒ素、アウキ
ルアルシン（たとえばメチルアルシン、エチルア
ルシンなど）、アルキルハロゲンアルシン（たと
えばジクロルメチルアルシン、ジクロルエチルア
ルシン、ジクロルプロピルアルシン、クロルジメ
チルアルシン、クロルジエチルアルシン、ブロム
ジメチルアルシン、ヨードジメチルアルシンな
ど）があげられる。
接触方法としては、たとえば固定層、移動層、
流動層などの公知の手段が用いられる。この場合
の接触温度は、200℃以下、好ましくは０〜150℃
であり、圧力は50Kg／cm2以下、好ましくは0.1〜
40Kg／cm2である。またガスの場合接触時間は25
℃、１Kg／cm2換算で1/10〜100秒、好ましくは1/5
〜80秒であり、液体の場合空間速度は25℃、１
Kg／cm2換算で1/10〜20hr-1、好ましくは1/5〜
10hr-1である。
以下に実施例を挙げて本発明をより具体的に説
明する。
実施例 １
BET比表面積1040m2／ｇの16〜24meshの活性
炭Ａに所定量の第一成分（硝酸銅）と第二成分
（アルカリ金属の硝酸塩、アルカリ土類金属の硝
酸塩、およびAl、Ti、Ｖ、Cr、Mn、Fe、Co、
Ni、Zn、Cd、Pbの硝酸塩（Ｖのみは硫酸塩））
とを溶解した水溶液を均一に散布した。
得られた添着物50mlを４cmφの石英ガラス製カ
ラムに充填し、窒素ガスを線流速10cm／secで流
通しながら昇温速度５℃／minで加熱し、300℃
で30分間焼成した。
得られた吸着剤中の各金属化合物の含量は、第
１表に示すように、活性炭１ｇ当りそれぞれ金属
として0.2〜2.0mg−原子であつた。
なお、対照として、前述と同様の方法で活性炭
Ａに各金属の硝酸塩を単独で添着し、さらに窒素
ガス中、300℃で30分間焼成した吸着剤を調製し
た。
このようにして得られた吸着剤Ａ〜Ｌおよび
〜〓〓の各20mlを1.6cmφのガラス製カラムに充填
し、AsH3−30ppm含有の30℃のガス（N2−
97.5vol％、H2O−2.5vol％）を線流速20cm／sec
で流通し、AsH3の破過吸着テストを行ない
AsH3がカラムからリークするまでの時間（破過
率が５％に達するまでの時間）を実測し結果を第
１表に示した。
The present invention relates to an arsine adsorbent and a method for treating arsine-containing fluids. Beverage carbon dioxide gas, coke oven gas, blast furnace gas, converter gas, petroleum distillate pyrolysis gas, natural gas, etc. contain arsine, which is extremely harmful to the human body even in minute amounts. It also exhibits a catalyst poisoning effect, which often causes problems in processes such as beverage processing and chemical reactions. As methods for removing arsine from gas, chemical cleaning methods using oxidizing solutions or adsorption methods using activated carbon have been proposed, but the removal effects are poor, and a more efficient arsine removal method has been desired. In view of these circumstances, the inventors of the present invention have made extensive studies and found that copper and alkali metals, alkaline earth metals, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Zn,
The present invention was completed based on the discovery that arsine in a fluid can be removed very efficiently by using an active substance containing Cd and Pb metals as oxides. That is, the present invention combines a fluid containing arsine and substantially no oxygen with an inorganic compound or organic acid salt of copper (hereinafter also referred to as the first component) and (a) an inorganic compound or organic acid of an alkali metal. salts, (b) inorganic compounds or organic acid salts of alkaline earth metals, and (c) Al, Ti,
After impregnating activated carbon with one or more types of inorganic compounds or organic acid salts of V, Cr, Mn, Fe, Co, Ni, Zn, Cd, and Pb (hereinafter also referred to as the second component)130
1. A method for treating an arsine-containing fluid, which comprises contacting an adsorbent made of activated carbon containing the above-mentioned metal components as oxides by firing at a temperature of 0.degree. C. or higher. The adsorbent used in the present invention can be produced by incorporating the first component and the second component as metal oxides into activated carbon. The activated carbon used in this case is manufactured by a known method using coal, coke, charcoal, coconut shell, resin, etc. as raw materials, and its specific surface area is
Any material may be used as long as it has an area of 200 to 2000 m 2 /g, and an appropriate shape is used depending on the gas processing method, such as spherical, cylindrical, crushed, powdered, or fibrous. The inorganic copper compound used in the present invention includes:
Examples of copper organic acid salts include carbonates, basic carbonates, nitrates, sulfates, phosphates, halides, oxides, and hydroxides; organic acid salts of copper include formates, acetates,
Examples include oxalate. Inorganic compounds of alkali metals include Li, Na,
Examples of K, Rb, and Cs include bicarbonates, carbonates, nitrates, borates, silicates, sulfates, halides, and hydroxides; examples of organic acid salts include formates, acetates, and oxalates. Examples include salts, benzoates, phenol salts, and sulfonic acid salts. In addition, as inorganic compounds of alkaline earth metals,
For example carbonates of Be, Mg, Ca, Sr and Ba,
Nitrates, sulfates, phosphates, halides, oxides, hydroxides, etc. Organic acid salts include formates,
Examples include acetate and oxalate. Al, Ti, V, Cr, Mn, Fe, Co, Ni, Zn,
Inorganic compounds of Cd and Pb include carbonates, hydrogen carbonates, nitrates, borates, silicates, sulfates, phosphates, halides, hydroxides, ammonium salts, and oxides of these metals. Examples of the organic acid salts include formates, acetates, oxalates, benzoates, phenol salts, and sulfonic acid salts. The adsorbent used in the present invention is activated carbon containing both a first component and a second component as metal oxides, but in this case, the second component is an inorganic compound or an organic acid salt of an alkali metal. [Hereinafter also referred to as component (a)] alone, an inorganic compound or organic acid salt of an alkaline earth metal [hereinafter also referred to as component (b)] alone or Al, Cr,
Inorganic compounds or organic acid salts of Ti, V, Mn, Fe, Co, Ni, Zn, Cd, Pb [hereinafter also referred to as component (c)] may be used alone, but among these, Two types of components may be used, such as component (a) and component (b), component (b) and component (c), or component (c) and component (a), or component (a) and component (a). It may also contain three components (b) and component (c) at the same time. In addition, two or more types of compounds may be used as the first component, and two or more different types of compounds within the same type of component may be used as the second component, for example, two different types of components within component (a). It may also be one using ivy component. In the adsorbent used in the present invention, the content of the first component in the activated carbon is 0.1 mg as metal per 1 g of activated carbon.
~3.0 mg-atoms, preferably ~2.0 mg-atoms
mg-atom, and the content of the second component is from 0.1 mg-atom to 5.0 mg-atom, preferably from 0.2 mg-atom to 4.0 mg-atom, as metal per gram of activated carbon. To impregnate activated carbon with each component, each component is dissolved or suspended in water (including acid or alkaline aqueous solutions), various solvents, etc., and the activated carbon is impregnated or sprayed at a temperature of approximately 130°C or less. This is carried out by evaporating and drying the water or solvent in the impregnated activated carbon. Firing is carried out by heating the impregnated activated carbon at a temperature of 130°C or higher in an atmosphere of inert gas, carbon dioxide gas, steam, combustion exhaust gas, etc. to thermally decompose the inorganic compounds or organic acid salts of each metal. Accordingly, each metal component is contained in activated carbon as an oxide. In the present invention, the fluid refers to a gas or a liquid, such as an inert gas, a reducing gas, or a liquefied form thereof. Examples of the inert gas or reducing gas include carbon dioxide gas, coke oven gas, blast furnace gas, converter gas, petroleum fraction pyrolysis gas, and natural gas. The method of the present invention is carried out by contacting the metal compound-containing activated carbon obtained above with a fluid containing arsine and substantially no oxygen.
Arsine, which is the substance to be removed in the present invention, is a hydrogen compound of arsenic and its hydrogen substituted with alkyl or halogen, such as arsenic hydride, aukylarsine (such as methylarsine, ethylarsine, etc.), alkylhalogenarsine (such as di- (chloromethylarsine, dichloroethylarsine, dichloropropylarsine, chlordimethylarsine, chlordiethylarsine, bromdimethylarsine, iododimethylarsine, etc.). Examples of contact methods include fixed layer, moving layer,
Known means such as a fluidized bed can be used. The contact temperature in this case is 200℃ or less, preferably 0 to 150℃
and the pressure is 50Kg/ cm2 or less, preferably 0.1~
It is 40Kg/ cm2 . In the case of gas, the contact time is 25
°C, 1/10 to 100 seconds in terms of 1Kg/ cm2 , preferably 1/5
~80 seconds, and in the case of liquid, the space velocity is 25℃, 1
1/10~20hr -1 in Kg/ cm2 , preferably 1/5~
10hr -1 . EXAMPLES The present invention will be explained in more detail with reference to Examples below. Example 1 A predetermined amount of the first component (copper nitrate) and second component (alkali metal nitrate, alkaline earth metal nitrate, Al, Ti, V, Cr, Mn, Fe, Co,
Nitrate of Ni, Zn, Cd, Pb (only V is sulfate)
An aqueous solution containing the above was evenly dispersed. 50ml of the obtained impregnated material was packed into a 4cmφ quartz glass column, heated at a temperature increase rate of 5°C/min while flowing nitrogen gas at a linear flow rate of 10cm/sec, and heated to 300°C.
Baked for 30 minutes. As shown in Table 1, the content of each metal compound in the obtained adsorbent was 0.2 to 2.0 mg atoms per gram of activated carbon. As a control, an adsorbent was prepared by impregnating activated carbon A with a nitrate of each metal alone in the same manner as described above, and then calcining it at 300° C. for 30 minutes in nitrogen gas. 20 ml each of adsorbents A to L and ~〓〓 obtained in this way were packed into a 1.6 cmφ glass column, and a gas (N 2 -
97.5vol%, H 2 O−2.5vol%) at a linear flow rate of 20cm/sec
distributed, and a breakthrough adsorption test of AsH 3 was conducted.
The time it took for AsH 3 to leak from the column (the time it took for the breakthrough rate to reach 5%) was actually measured, and the results are shown in Table 1.
【表】【table】
【表】【table】
Claims (1)
流体を、銅の無機化合物または有機酸塩と(a)
アルカリ金属の無機化合物または有機酸塩、(b)ア
ルカリ土類金属の無機化合物または有機酸塩およ
び(c)Al、Ti、Ｖ、Cr、Mn、Fe、Co、Ni、Zn、
Cd、Pbの無機化合物または有機酸塩の一種以上
とを活性炭に添着した後130℃以上の温度で焼成
することにより上記およびの金属成分を酸化
物として活性炭に含有せしめてなる吸着剤に接触
させることを特徴とするアルシン含有流体の処理
方法。1. A fluid containing arsine and substantially no oxygen is mixed with an inorganic compound or an organic acid salt of copper (a)
Inorganic compounds or organic acid salts of alkali metals, (b) inorganic compounds or organic acid salts of alkaline earth metals, and (c) Al, Ti, V, Cr, Mn, Fe, Co, Ni, Zn,
One or more inorganic compounds or organic acid salts of Cd and Pb are impregnated onto activated carbon, and then fired at a temperature of 130°C or higher to bring the metal components mentioned above into contact with the activated carbon as oxides. A method for treating an arsine-containing fluid, characterized by:
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58034923A JPS59160535A (en) | 1983-03-03 | 1983-03-03 | Adsorbent for arsine and treatment of fluid containing arsine |
| CA000446846A CA1216136A (en) | 1983-03-03 | 1984-02-06 | Method for removal of poisonous gases |
| US06/581,367 US4532115A (en) | 1983-03-03 | 1984-02-17 | Method for removal of poisonous gases |
| EP84301379A EP0121339B1 (en) | 1983-03-03 | 1984-03-02 | Method for removal of poisonous gases |
| DE8484301379T DE3467096D1 (en) | 1983-03-03 | 1984-03-02 | Method for removal of poisonous gases |
| SG22/90A SG2290G (en) | 1983-03-03 | 1990-01-15 | Method for removal of poisonous gases |
| HK122/90A HK12290A (en) | 1983-03-03 | 1990-02-15 | Method for removal of poisonous gases |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58034923A JPS59160535A (en) | 1983-03-03 | 1983-03-03 | Adsorbent for arsine and treatment of fluid containing arsine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59160535A JPS59160535A (en) | 1984-09-11 |
| JPH0424092B2 true JPH0424092B2 (en) | 1992-04-24 |
Family
ID=12427728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58034923A Granted JPS59160535A (en) | 1983-03-03 | 1983-03-03 | Adsorbent for arsine and treatment of fluid containing arsine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59160535A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6071040A (en) * | 1983-09-27 | 1985-04-22 | Takeda Chem Ind Ltd | Noxious gas adsorbent |
| JPS60238144A (en) * | 1984-05-11 | 1985-11-27 | Idemitsu Petrochem Co Ltd | Arsenic compound removing agent |
| US7465692B1 (en) | 2000-03-16 | 2008-12-16 | Pall Corporation | Reactive media, methods of use and assemblies for purifying |
| CN108014742B (en) * | 2017-11-29 | 2021-01-05 | 北京科技大学 | Method for selectively and deeply removing trace silver ions in tail liquid |
-
1983
- 1983-03-03 JP JP58034923A patent/JPS59160535A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59160535A (en) | 1984-09-11 |
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