JPH0464734B2 - - Google Patents
Info
- Publication number
- JPH0464734B2 JPH0464734B2 JP58176092A JP17609283A JPH0464734B2 JP H0464734 B2 JPH0464734 B2 JP H0464734B2 JP 58176092 A JP58176092 A JP 58176092A JP 17609283 A JP17609283 A JP 17609283A JP H0464734 B2 JPH0464734 B2 JP H0464734B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- component
- activated carbon
- adsorbent
- gas
- 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 54
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 21
- 239000003463 adsorbent Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- 239000012433 hydrogen halide Substances 0.000 claims description 9
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 9
- 229910052793 cadmium Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052745 lead Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000005749 Copper compound Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 150000001880 copper compounds Chemical class 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- -1 hydrogen halides Chemical class 0.000 description 15
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 150000004679 hydroxides Chemical class 0.000 description 6
- 150000002823 nitrates Chemical class 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 150000002484 inorganic compounds Chemical class 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 150000004675 formic acid derivatives Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 150000001339 alkali metal compounds Chemical class 0.000 description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 150000003891 oxalate salts Chemical class 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 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
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 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
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000002407 reforming Methods 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
本発明はハロゲンおよび／またはハロゲン化水
素を除去するための吸着剤および該水素化合物を
含有する気体を処理する方法に関する。
石油化学工場、化学工業のプロセスガス、製鉄
所などの副生ガス、電解水素、改質用水蒸気、そ
の他各種の排ガスなどにはハロゲン、ハロゲン化
水素が含まれており、このハロゲン、ハロゲン化
水素は微量でも人体に極めて有害であり、装置な
どの金属面に対して腐食作用がありまた触媒毒作
用も呈するので、化学反応などの工程で問題とな
ることが多い。
ガス中のハロゲン、ハロゲン化水素を除去する
方法として、アルカリ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、効率のよい吸着
剤が望まれていた。
本発明者らは、このような実情に鑑み、鋭意検
討した結果、活性炭に銅化合物とSr、Mg、Ca、
Al、Ti、Mn、Fe、Co、Ni、Zn、Cd、Pbの金
属化合物を含有せしめることによつて、ガス中の
ハロゲン、ハロゲン化水素を非常に効率よく除去
できることを見出し、本発明を完成した。
すなわち本発明は、
１ 銅化合物と下記(a)、(b)および(c)のいずれか一
つとを活性炭に含有せしめてなるハロゲンおよ
び／またはハロゲン化水素を除去するための吸
着剤
２ ハロゲンおよび／またはハロゲン化水素を含
有する気体を、銅化合物（以下第一成分という
こともある）と下記(a)、(b)および(c)のいずれか
一つとを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該気体からハロゲン
および／またはハロゲン化水素を除去する方法
(a) Sr、Mg、Ca、Al、Ti、Mn、Fe、Co、
Ni、Zn、CdおよびPbの化合物の一種
(b) Mgの化合物およびCoの化合物の双方
(c) Caの化合物およびNiの化合物の双方
（以下第二成分ということもある）
である。
本発明の吸着剤は活性炭に前記第一成分および
第二成分を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。
本発明において第一成分として用いられる銅化
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、水酸化物などの無機酸塩または無機化合物、
ギ酸塩、酢酸塩、シユウ酸塩などの有機酸塩など
が挙げられる。
第二成分の一つであるMg、Ca、Srの化合物と
してはたとえばこれらの金属の炭酸塩、硝酸塩、
硫酸塩、リン酸塩、ハロゲン化物、酸化物、水酸
化物などの無機塩酸または無機化合物、ギ酸塩、
酢酸塩、シユウ酸塩などの有機酸塩などがあげら
れる。
他の第二成物であるAl、Ti、Ｖ、Cr、Mn、
Fe、Co、Ni、Zn、Cd、Pbの化合物としてはこ
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、酸化物などの無
機酸塩または無機化合物、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
ン酸類の塩などの有機酸塩などが挙げられる。ま
た第二成分としてはMgの化合物とCoの化合物を
併用してもよく、Caの化合物のNiの化合物を併
用してもよい。
本発明の吸着剤は活性炭に第一成分および第二
成分の双方を含有せしめたものであるがさらに第
三成分としてアルカリ金属化合物またはCr、Ｖ
の化合物（以下第三成分という）を含有せしめて
もよい。アルカリ金属化合物としては、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、水酸化物などの無機化合物、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の有機酸塩などが挙げ
られる。Cr、Ｖの化合物としてはこれらの炭酸
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、酸化物などの無機塩酸または無機
化合物、ギ塩酸、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の
有機酸塩などが挙げられる。本発明の吸着剤には
第二成分、第三成分として、Sr、Mg、Ca化合物
〔以下成分(a)ということもある〕単独またはAl、
Ti、Mn、Fe、Co、Ni、Zn、Cd、Pbの化合物
〔以下成分(c)ということもある〕単独を含有せし
めたものであつてもよいが、成分(b)と第三成分、
または成分(a)と第三成分のように二種の成分を含
有せしめたものでもよい。
金属化合物含有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〜2.0mg−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。第三成分を添加する場
合、その含量は活性炭１ｇ当たり金属として0.1
ｍ−原子〜5.0mg−原子、好ましくは0.2mg−原子
〜4.0mg−原子である。
本発明の吸着剤は活性炭に各成分を担持もしく
は添着せしめたものでもよく、また活性炭原料に
各成分を添加したのち、これを賦活して得られる
ものでもよい。また第一成分、第二成分および必
要により第三成分の一部を活性炭原料に添加して
これを賦活し、これに残りの成分を添着せしめた
ものでもよい。各成分を活性炭に添着する場合
は、添着後乾燥または焼成するのがよい。
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
含浸または散布する方法が考えられる。また、前
記の調製法において、乾燥は、約130℃以下の温
度で、添着活性炭中の水または溶媒を蒸発させる
工程をいい、また焼成は、約130℃以上の温度で
乾燥した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、金属化
合物の一部または全部を熱分解させる工程をい
う。
上記方法において、第一成分、第二成分として
酸化物以外のものを活性炭に添着した場合は、添
着後乾燥または焼成など熱処理するのがよく、ま
た第一成分、第二成分を活性炭に添着して熱処理
をしないときは、第一成分、第二成分は酸化物を
用いるのがよい。第三成分としてアルカリ金属の
水酸化物、炭酸塩、重炭酸塩以外のアルカリ金属
化合物を活性炭に添着した場合には添着後乾燥ま
たは焼成などの熱処理をするのがよく、アルカリ
金属化合物を添着したのち熱処理をしない場合に
はアルカリ金属化合物として水酸化物、炭酸塩、
重炭酸塩を用いるのがよい。
本発明において、ハロゲンとはF2、Cl2Br2お
よびI2であり、ハロゲン化水素とはHF、HCl、
HBrおよびHIである。
本発明を用いてガス中のハロゲン、ハロゲン化
水素を除去するには、ハロゲン、ハロゲン化水素
を含有するガスと吸着剤とを接触させればよい。
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、600℃以下、好ましくは０〜300℃
であり、圧力は300Kg／cm2以下、好ましくは0.1〜
250Kg／cm2である。また接触時間は25℃、１Kg／
cm2換算で1/10〜100秒、好ましくは1/5〜80秒であ
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1150m2／ｇの16〜24meshの活性
炭A0に所定量の第一成分（硝酸銅）と第二成分、
第三成分（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、Cr、Mn、Fe、
Co、Ni、Zn、Cd、Pbの硝酸塩）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
通しながら昇音速度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
A0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の各15mlを1.6
cmφのガラス製カラムに充填し、HCl−20ppmお
よびCl2−10ppm含有のガス（N2−97.5vol％、
H2O−2.5vol％）を線流速40cm／sec（30℃換算）、
温度200℃で流通し、HCl−Cl2（全Cl換算）の除
去率の経時変化を調べ結果を第１表に示した。
実施例 ２
実施例１の吸着剤A0、A1、A6、B1、C4、C7、
D6、D9、D10、D11およびD12の各15mlを1.6cmφ
のガラス製カラムに充填し、HCl−20ppmおよび
Cl2−10ppm含有の30℃のガス（H2−8vol％、N2
−92vol％）を線流速40cm／secで流通し、HCl−
Cl2（全Cl換算）の除去率の経時変化を調べ結果を
第２表に示した。
The present invention relates to an adsorbent for removing halogens and/or hydrogen halides and a method for treating gases containing said hydrogen compounds. Process gases from petrochemical plants and chemical industries, by-product gases from steel plants, electrolyzed hydrogen, reforming steam, and various other exhaust gases contain halogens and hydrogen halides. Even in minute amounts, it is extremely harmful to the human body, corrosive to metal surfaces of equipment, etc., and also poisons catalysts, so it often poses a problem in processes such as chemical reactions. Chemical cleaning methods using alkaline solutions or adsorption methods using activated carbon have been proposed as methods for removing halogens and hydrogen halides from gas, but the removal effects are poor, and more efficient adsorbents are desired. Ta. In view of these circumstances, the inventors of the present invention have made extensive studies and found that activated carbon contains copper compounds, Sr, Mg, Ca,
It was discovered that halogens and hydrogen halides in gas can be removed very efficiently by containing metal compounds of Al, Ti, Mn, Fe, Co, Ni, Zn, Cd, and Pb, and the present invention was completed. did. That is, the present invention provides: 1. An adsorbent for removing halogen and/or hydrogen halide, which is made by containing a copper compound and any one of the following (a), (b), and (c) in activated carbon. An adsorbent in which activated carbon contains a copper compound (hereinafter also referred to as the first component) and any one of the following (a), (b), and (c) for a gas containing hydrogen halide/or hydrogen halide. A method for removing halogen and/or hydrogen halide from the gas, characterized by bringing the gas into contact with (a) Sr, Mg, Ca, Al, Ti, Mn, Fe, Co,
A type of compound of Ni, Zn, Cd, and Pb (b) Both a Mg compound and a Co compound (c) Both a Ca compound and a Ni compound (hereinafter sometimes referred to as the second component). The adsorbent of the present invention can be manufactured by incorporating the first component and the second component 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. Examples of the copper compound used as the first component in the present invention include carbonates, basic carbonates,
inorganic acid salts or inorganic compounds such as nitrates, sulfates, phosphates, halides, oxides, hydroxides;
Examples include organic acid salts such as formates, acetates, and oxalates. Compounds of Mg, Ca, and Sr, which are one of the second components, include carbonates, nitrates, and
Inorganic hydrochloric acid or inorganic compounds such as sulfates, phosphates, halides, oxides, hydroxides, formates,
Examples include organic acid salts such as acetate and oxalate. Other secondary components Al, Ti, V, Cr, Mn,
Compounds of Fe, Co, Ni, Zn, Cd, and Pb include carbonates, hydrogen carbonates, nitrates, borates, silicates, sulfates, phosphates, halides, hydroxides, Examples include inorganic acid salts or inorganic compounds such as ammonium salts and oxides, and organic acid salts such as formates, acetates, oxalates, benzoates, salts of phenols, and salts of sulfonic acids. Further, as the second component, a Mg compound and a Co compound may be used together, or a Ca compound and a Ni compound may be used together. The adsorbent of the present invention contains activated carbon containing both a first component and a second component, and further contains an alkali metal compound or Cr, V as a third component.
(hereinafter referred to as the third component) may be included. Alkali metal compounds include Li, Na,
Inorganic compounds of K, Rb, Cs such as bicarbonates, carbonates, nitrates, borates, silicates, sulfates, halides, hydroxides, formates, acetates, oxalates, benzoates Examples include organic acid salts such as salts, phenol salts, and sulfonic acid salts. Compounds of Cr and V include carbonates, hydrogen carbonates, nitrates, borates, silicates,
Inorganic hydrochloric acid or inorganic compounds such as sulfates, phosphates, halides, hydroxides, ammonium salts, oxides, formic acid, acetate, oxalate, benzoate, salts of phenols, salts of sulfonic acids Examples include organic acid salts such as. The adsorbent of the present invention contains Sr, Mg, Ca compounds (hereinafter also referred to as component (a)) alone or Al,
A compound of Ti, Mn, Fe, Co, Ni, Zn, Cd, Pb (hereinafter also referred to as component (c)) may be contained alone, but component (b) and a third component,
Alternatively, it may contain two types of components, such as component (a) and a third component. The content of the first component in the activated carbon containing a metal compound is from 0.1 mg-atom to 3.0 mg-atom, preferably from 0.2 mg-atom to 2.0 mg-atom, as metal per gram of activated carbon, and the content of the second component is from 0.2 mg-atom to 2.0 mg-atom per gram of activated carbon. as metal
0.1 mg-atom to 5.0 mg-atom, preferably 0.2 mg-atom to 4.0 mg-atom. If a third component is added, its content should be 0.1 as metal per gram of activated carbon.
m-atoms to 5.0 mg-atoms, preferably 0.2 mg-atoms to 4.0 mg-atoms. The adsorbent of the present invention may be one in which each component is supported or impregnated on activated carbon, or it may be obtained by adding each component to an activated carbon raw material and then activating this. Alternatively, the first component, the second component, and if necessary, a part of the third component may be added to the activated carbon raw material to activate it, and the remaining components may be impregnated therewith. When each component is impregnated onto activated carbon, it is preferable to dry or bake it after impregnation. Possible methods for impregnating activated carbon with each component include impregnating or spraying activated carbon with a solution in which each component is dissolved or suspended in water (including acid or alkaline aqueous solutions), various solvents, or the like. In the above preparation method, drying refers to the step of evaporating the water or solvent in the impregnated activated carbon at a temperature of about 130°C or lower, and calcination refers to the step of evaporating the impregnated activated carbon that has been dried at a temperature of about 130°C or higher. A process in which part or all of a metal compound is thermally decomposed by heating in an atmosphere of active gas, carbon dioxide, steam, combustion exhaust gas, etc. In the above method, when substances other than oxides are impregnated onto activated carbon as the first and second components, it is recommended to heat-treat the activated carbon by drying or firing after impregnation. When heat treatment is not performed, it is preferable to use oxides as the first and second components. When an alkali metal compound other than alkali metal hydroxide, carbonate, or bicarbonate is impregnated onto activated carbon as a third component, it is best to perform heat treatment such as drying or calcination after impregnation. If no heat treatment is performed later, hydroxides, carbonates,
It is better to use bicarbonate. In the present invention, halogens include F 2 , Cl 2 Br 2 and I 2 , and hydrogen halides include HF, HCl,
HBr and HI. In order to remove halogen and hydrogen halide from a gas using the present invention, it is sufficient to bring the gas containing halogen and hydrogen halide into contact with an adsorbent. 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 600℃ or less, preferably 0 to 300℃
and the pressure is 300Kg/ cm2 or less, preferably 0.1~
It is 250Kg/ cm2 . The contact time is 25℃, 1Kg/
The time is 1/10 to 100 seconds, preferably 1/5 to 80 seconds in terms of cm2 . EXAMPLES The present invention will be explained in more detail with reference to Examples below. Example 1 Predetermined amounts of the first component (copper nitrate) and the second component were added to 16 to 24 mesh activated carbon A0 with a BET specific surface area of 1150 m 2 /g.
Third components (alkali metal nitrates, alkaline earth metal nitrates, and Al, Ti, Cr, Mn, Fe,
An aqueous solution containing nitrates of Co, Ni, Zn, Cd, and Pb was uniformly sprayed. 50ml of the obtained impregnated material was packed into a 4cmφ quartz glass column, heated at a sound rise 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, activated carbon was added using the same method as described above.
An adsorbent was prepared by impregnating A 0 with a single nitrate of each metal and then calcining it at 300°C for 30 minutes in nitrogen gas. Each 15 ml of the adsorbent thus obtained is 1.6
A cmφ glass column was packed with a gas containing HCl-20ppm and Cl2-10ppm ( N2-97.5vol %,
H 2 O−2.5vol%) at a linear flow rate of 40cm/sec (30℃ conversion),
The sample was circulated at a temperature of 200° C., and the change in removal rate of HCl-Cl 2 (in terms of total Cl) over time was investigated, and the results are shown in Table 1. Example 2 Adsorbent of Example 1 A 0 , A 1 , A 6 , B 1 , C 4 , C 7 ,
15ml each of D 6 , D 9 , D 10 , D 11 and D 12 to 1.6cmφ
Filled in a glass column with HCl−20ppm and
Gas at 30°C containing Cl 2 −10 ppm (H 2 −8 vol%, N 2
-92 vol%) at a linear flow rate of 40 cm/sec, HCl-
The changes over time in the removal rate of Cl 2 (in terms of total Cl) were investigated and the results are shown in Table 2.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
実施例 ３
実施例１の吸着剤A0、A1、C7、D6、D10およ
びD12の各15mlを1.6cmφのガラス製カラムに充填
し、HCl−20ppm、Cl2−10ppm含有のガス（N2
−97.5vol％、H2O−2.5vol％）、HBr−20ppm、
Br2−10ppm含有のガス（N2−97.5vol％、H2O
−2.5vol％）、およびHI−20ppm、I2−10ppm含
有のガス（N2−97.5vol％、H2O−2.5vol％）を
それぞれ線流速40cm／sec（30℃換算）、温度250℃
で流通し、HCl−Cl2（全Cl換算）HBr−Br2（全
Br換算）およびHI−I2（全Ｉ換算）がカラムから
リークするまでの時間（それぞれの除去率が95％
に達するまでの時間）を求め、結果を第３表にま
とめた。[Table] Example 3 15 ml each of the adsorbents A 0 , A 1 , C 7 , D 6 , D 10 and D 12 of Example 1 were packed into a 1.6 cmφ glass column, and HCl−20ppm, Cl 2 − Gas containing 10ppm ( N2
−97.5vol%, H2O −2.5vol%), HBr−20ppm,
Gas containing Br 2 −10ppm (N 2 −97.5vol%, H 2 O
-2.5vol%), and gases containing HI-20ppm and I2-10ppm ( N2-97.5vol %, H2O -2.5vol%) at a linear flow rate of 40cm/sec (30℃ conversion) and a temperature of 250℃.
HCl−Cl 2 (total Cl equivalent) HBr−Br 2 (total Cl)
Br conversion) and HI-I 2 (total I conversion) leak from the column (each removal rate is 95%).
The results are summarized in Table 3.
Claims (1)
つとを活性炭に含有せしめてなるハロゲンおよ
び／またはハロゲン化水素を除去するための吸着
剤 (a) Sr、Mg、Ca、Al、Ti、Mn、Fe、Co、Ni、
Zn、CdおよびPbの化合物の一種 (b) Mgの化合物およびCoの化合物の双方 (c) Caの化合物およびNiの化合物の双方。 ２ ハロゲンおよび／またはハロゲン化水素を含
有する気体を、銅化合物と下記(a)、(b)および(c)の
いずれか一つとを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該気体からハロ
ゲンおよび／またはハロゲン化水素を除去する方
法 (a) Sr、Mg、Ca、Al、Ti、Mn、Fe、Co、Ni、
Zn、CdおよびPbの化合物の一種 (b) Mgの化合物およびCoの化合物の双方 (c) Caの化合物およびNiの化合物の双方。[Scope of Claims] 1. An adsorbent (a) for removing halogen and/or hydrogen halide, comprising activated carbon containing a copper compound and any one of the following (a), (b), and (c). ) Sr, Mg, Ca, Al, Ti, Mn, Fe, Co, Ni,
One of the compounds of Zn, Cd and Pb (b) Both the compound of Mg and the compound of Co (c) The compound of Ca and the compound of Ni. 2. A gas containing halogen and/or hydrogen halide is brought into contact with an adsorbent comprising activated carbon containing a copper compound and any one of the following (a), (b) and (c). Method for removing halogen and/or hydrogen halide from the gas (a) Sr, Mg, Ca, Al, Ti, Mn, Fe, Co, Ni,
One of the compounds of Zn, Cd and Pb (b) Both the compound of Mg and the compound of Co (c) The compound of Ca and the compound of Ni.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58176092A JPS6068051A (en) | 1983-09-22 | 1983-09-22 | Harmful gas adsorbent |
| US06/653,091 US4594231A (en) | 1983-09-22 | 1984-09-21 | Method for removal of poisonous gases |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58176092A JPS6068051A (en) | 1983-09-22 | 1983-09-22 | Harmful gas adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6068051A JPS6068051A (en) | 1985-04-18 |
| JPH0464734B2 true JPH0464734B2 (en) | 1992-10-15 |
Family
ID=16007561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58176092A Granted JPS6068051A (en) | 1983-09-22 | 1983-09-22 | Harmful gas adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6068051A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4702749A (en) * | 1986-06-24 | 1987-10-27 | Air Products And Chemicals, Inc. | Technique for surface oxidation of activated carbon |
| JP3716030B2 (en) * | 1996-02-29 | 2005-11-16 | 日本パイオニクス株式会社 | How to clean harmful gases |
| JP4276333B2 (en) * | 1998-09-22 | 2009-06-10 | 日本パイオニクス株式会社 | Exhaust gas purification method |
| US8585808B2 (en) * | 2010-11-08 | 2013-11-19 | 3M Innovative Properties Company | Zinc oxide containing filter media and methods of forming the same |
| CN111617739B (en) * | 2020-05-09 | 2022-06-28 | 齐鲁工业大学 | Al-Mn modified biomass charcoal and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55104633A (en) * | 1979-02-05 | 1980-08-11 | Bergwerksverband Gmbh | Method of separating hydrogen chloride in combustion gas |
-
1983
- 1983-09-22 JP JP58176092A patent/JPS6068051A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55104633A (en) * | 1979-02-05 | 1980-08-11 | Bergwerksverband Gmbh | Method of separating hydrogen chloride in combustion gas |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6068051A (en) | 1985-04-18 |
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