JP2002119851A - Carbon monoxide adsorbent and method of manufacturing for the same - Google Patents
Carbon monoxide adsorbent and method of manufacturing for the sameInfo
- Publication number
- JP2002119851A JP2002119851A JP2000312780A JP2000312780A JP2002119851A JP 2002119851 A JP2002119851 A JP 2002119851A JP 2000312780 A JP2000312780 A JP 2000312780A JP 2000312780 A JP2000312780 A JP 2000312780A JP 2002119851 A JP2002119851 A JP 2002119851A
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- JP
- Japan
- Prior art keywords
- carbon monoxide
- adsorbent
- carbon
- monoxide adsorbent
- copper
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、一酸化炭素含有ガ
スから一酸化炭素を吸着して分離回収する一酸化炭素吸
着剤及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon monoxide adsorbent for adsorbing and separating carbon monoxide from a gas containing carbon monoxide and a method for producing the same.
【０００２】[0002]
【従来の技術】従来、製鉄所や石油化学工場などで副生
するガス、石油及び天然ガスを改質して得られる改質ガ
ス又は部分酸化ガスなどには一酸化炭素が多く含有され
ており、これらのガスを原料ガスとして一酸化炭素が回
収され化学原料用として消費されている。2. Description of the Related Art Conventionally, reformed gas or partially oxidized gas obtained by reforming gas by-produced in steel works and petrochemical plants, petroleum and natural gas, etc. contain a large amount of carbon monoxide. Carbon monoxide is recovered using these gases as raw material gases and consumed as chemical raw materials.
【０００３】一酸化炭素含有の原料ガスから一酸化炭素
を回収する方法としては、以前から多くの方法が提案さ
れており、その例として、銅化合物溶液による吸収法、
原料ガスを液化して温度差で分離回収する深冷分離法及
び加圧下で一酸化炭素を吸着し、減圧により一酸化炭素
を放出分離させて一酸化炭素を回収する圧力スイング式
吸着分離法（Ｐｒｅｓｓｕｒｅ Ｓｗｉｎｇ Ａｄｓｏ
ｒｐｔｉｏｎ：ＰＳＡ法）などが知られている。[0003] Many methods have been proposed for recovering carbon monoxide from a carbon monoxide-containing raw material gas. Examples of such methods include an absorption method using a copper compound solution,
A cryogenic separation method in which raw material gas is liquefied and separated and recovered at a temperature difference, and a pressure swing adsorption separation method in which carbon monoxide is adsorbed under pressure and carbon monoxide is released and separated under reduced pressure to recover carbon monoxide ( Pressure Swing Adso
rption (PSA method) is known.
【０００４】前記の方法において、吸収法や深冷分離法
は古くから使用されている方法であるが、装置構成が極
めて複雑で運転管理が煩雑となり、高圧のため動力費や
設備費が嵩み、また、運転条件が過酷であるため装置の
腐食が惹起されやすい問題があるため、近年は圧力スイ
ング式吸着分離法（以下ＰＳＡ法という。）が多く採用
されている。In the above method, the absorption method and the cryogenic separation method have been used for a long time. However, the equipment configuration is extremely complicated, the operation management becomes complicated, and the power and equipment costs are increased due to high pressure. In addition, since the operating conditions are severe, there is a problem that the corrosion of the apparatus is likely to be caused. Therefore, in recent years, a pressure swing type adsorption separation method (hereinafter, referred to as a PSA method) is often used.
【０００５】前記ＰＳＡ法において使用される吸着剤と
しては、特開昭５９−１０５８４１号公報、特開昭５９
−１３６１３４号公報及び特開昭６２−１１４６４６号
公報などに、活性炭にハロゲン化銅（Ｉ）や酸化銅
（Ｉ）などの銅化合物を担持した吸着剤が開示されてお
り、また、特開昭６２−２３７９４２号公報には、ハロ
ゲン化銅化合物とハロゲン化アルミニウムとの混合物を
活性炭に担持した吸着剤が開示されている。The adsorbents used in the PSA method are disclosed in JP-A-59-105841 and JP-A-59-105584.
JP-A-136134 and JP-A-62-114646 disclose an adsorbent in which a copper compound such as copper (I) halide or copper (I) oxide is supported on activated carbon. JP-A-62-237942 discloses an adsorbent in which a mixture of a copper halide compound and an aluminum halide is supported on activated carbon.
【０００６】[0006]
【発明が解決しようとする課題】前記従来の活性炭に銅
化合物を担持した吸着剤においては、木材、ヤシ殻、石
炭、石油系ピッチ、セルロ−ス繊維又は化学繊維などを
原料とし、その原料を加熱して炭化処理したのち、不活
性ガスなどで賦活処理して製造された活性炭粒子が用い
られているが、それらの活性炭粒子は摩耗しやすいた
め、粉化しやすく、充填層において圧密化や粒子間の閉
塞を起こして、被処理ガスの流通抵抗を増大させたり、
また、飛散して処理ガスに混入するなどの問題があり、
また、一酸化炭素の吸着物質として銅塩化物を担持した
場合などには、銅塩化物と水分とが反応しやすくなり、
塩酸を生成して装置を構成する材料を腐食させる問題も
ある。In the conventional adsorbent in which a copper compound is supported on activated carbon, wood, coconut shell, coal, petroleum pitch, cellulose fiber or chemical fiber is used as a raw material, and the raw material is used as the raw material. Activated carbon particles manufactured by heating and carbonizing and then activating with an inert gas are used.These activated carbon particles are liable to be abraded, so they are easily powdered. Cause blockage between them, increasing the flow resistance of the gas to be treated,
In addition, there are problems such as scattering and mixing into the processing gas,
In addition, when copper chloride is supported as an adsorbing substance of carbon monoxide, the copper chloride easily reacts with moisture,
There is also a problem that the hydrochloric acid is generated to corrode the material constituting the device.
【０００７】本発明は、前記の問題に鑑みてなされたも
のであり、一酸化炭素吸着剤において、耐摩擦強度及び
耐圧強度が高いため、極めて摩耗及び粉化しにくく、ま
た、一酸化炭素吸着能の高い一酸化炭素吸着剤とその一
酸化炭素吸着剤を製造する方法を提供する目的で成され
たものである。[0007] The present invention has been made in view of the above-mentioned problems, and the carbon monoxide adsorbent is extremely resistant to abrasion and powdering because of its high friction resistance and pressure resistance. The purpose of the present invention is to provide a carbon monoxide adsorbent having a high carbon monoxide and a method for producing the carbon monoxide adsorbent.
【０００８】[0008]
【課題を解決するための手段】前記目的を達成するため
の本発明の要旨は、請求項１に記載の発明においては、
イオン交換樹脂から製造された活性炭に少なくとも銅化
合物を担持したことを特徴とする一酸化炭素吸着剤であ
る。前記一酸化炭素吸着剤は従来の活性炭を用いた一酸
化炭素吸着剤よりも、耐摩耗強度が約10倍、耐圧強度が
約５０倍、一酸化炭素吸着能も約１．２倍に向上する。The gist of the present invention for achieving the above object is as follows.
A carbon monoxide adsorbent characterized in that at least a copper compound is supported on activated carbon produced from an ion exchange resin. The carbon monoxide adsorbent has an abrasion resistance strength of about 10 times, a pressure resistance strength of about 50 times, and a carbon monoxide adsorption capacity of about 1.2 times that of a conventional carbon monoxide adsorbent using activated carbon. .
【０００９】また、請求項２に記載の発明においては、
イオン交換樹脂を不活性ガス雰囲気で７００〜１０００
℃に加熱して炭化処理し、炭化処理して得られた炭化物
を二酸化炭素と窒素の雰囲気で７００〜１０００℃に加
熱して賦活処理して活性炭を製造し、その活性炭に少な
くとも銅化合物溶液を含浸し、その含浸活性炭を乾燥し
て少なくとも銅化合物を担持した一酸化炭素吸着剤を得
ることを特徴とする一酸化炭素吸着剤の製造方法であ
る。前記の製造方法により、従来の活性炭を用いた一酸
化炭素吸着剤よりも、耐摩耗強度が約10倍、耐圧強度が
約５０倍、一酸化炭素吸着能も約１．２倍に向上した一
酸化炭素吸着剤を得ることができる。Further, in the invention according to claim 2,
700-1000 ion exchange resin in an inert gas atmosphere
C. and carbonized by heating to a temperature of 700 to 1000 ° C. in an atmosphere of carbon dioxide and nitrogen to produce activated carbon, and at least a copper compound solution is added to the activated carbon. A method for producing a carbon monoxide adsorbent, comprising impregnating and drying the impregnated activated carbon to obtain a carbon monoxide adsorbent carrying at least a copper compound. According to the above-described production method, the abrasion resistance strength, the pressure resistance strength about 50 times, and the carbon monoxide adsorption capacity are improved about 1.2 times as compared with the conventional carbon monoxide adsorbent using activated carbon. A carbon oxide adsorbent can be obtained.
【００１０】なお、前記イオン交換樹脂としては、スチ
レン系強酸性陽イオン交換樹脂（Ｒ−ＳＯ3Ｈ）、石炭
酸系強酸性陽イオン交換樹脂（Ｒ−ＳＯ3Ｈ，Ｒ−Ｏ
Ｈ）、中酸性陽イオン交換樹脂（Ｒ−ＣＯＯＨ，Ｒ−Ｏ
Ｈ）及び弱酸性陽イオン交換樹脂（Ｒ−ＰＯ2Ｈ2）など
を用いることができるが、より耐久性が大きいことから
スチレン系強酸性陽イオン交換樹脂を用いるのが好まし
い。As the ion exchange resin, a styrene-based strongly acidic cation exchange resin (R-SO3H) and a carboxylate-based strongly acidic cation exchange resin (R-SO3H, RO)
H), a medium acidic cation exchange resin (R-COOH, RO)
H) and a weakly acidic cation exchange resin (R-PO2H2) can be used, but a styrene-based strongly acidic cation exchange resin is preferably used because of its higher durability.
【００１１】また、担持される銅化合物としては、Ｉ価
又はＩＩ価の塩化銅、臭化銅などのハロゲン化銅化合
物、酸化銅、チオシアン酸銅、硝酸銅又は炭酸銅などが
用いられ、また、それらの銅化合物の少なくとも１成分
とハロゲン化アルミニウム又はハロゲン化鉄、ハロゲン
化ニッケルなどのＶIII属金属などと混合して用いても
よいが、吸着能が高く、担持しやすいため、塩化銅
（Ｉ）を用いるのが好ましい。As the copper compound to be supported, copper halides such as I- or II-valent copper chloride and copper bromide, copper oxide, copper thiocyanate, copper nitrate and copper carbonate are used. It is also possible to use a mixture of at least one component of these copper compounds with an aluminum halide or an iron halide, a Group VIII metal such as nickel halide, or the like. However, copper chloride ( It is preferred to use I).
【００１２】[0012]
【発明の実施の形態】以下に、実施例を挙げて本発明の
実態の形態を具体的に説明する。しかしこれらの実施例
は本発明を説明するために示すものであり、発明の範囲
を限定するものではない。なお、図１は本発明の一酸化
炭素吸着剤と従来の一酸化炭素吸着剤との一酸化炭素吸
着能を比較した吸着等温線ク゛ラフである。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be specifically described with reference to examples. However, these examples are provided to illustrate the present invention and do not limit the scope of the invention. FIG. 1 is an adsorption isotherm graph comparing the carbon monoxide adsorbing ability of the carbon monoxide adsorbent of the present invention and a conventional carbon monoxide adsorbent.
【００１３】[0013]
【実施例】スチレン・ジビニルベンゼン共重合体をスル
ホン化したスチレン強酸性陽イオン交換樹脂を原料とし
て、窒素気流中で炭化処理を行った。なお、炭化処理は
温度を５℃／分で上昇させ、８００℃まで昇温し、その
温度で６０分保持した。炭化処理を行って得られた炭化
物を水洗及び乾燥し、乾燥炭化物を二酸化炭素と窒素の
混合気流中で賦活処理して活性炭を製造した。なお、賦
活処理は温度を５℃／分で上昇させ、９００℃まで昇温
し、その温度で６０分保持した。賦活処理を行って得ら
れた活性炭を水洗及び乾燥し、窒素雰囲気中で塩酸に溶
解した塩化銅（Ｉ）溶液に浸漬して含浸させ、その含浸
活性炭を乾燥して銅化合物を担持した一酸化炭素吸着剤
を得た。なお、塩化銅（Ｉ）溶液は、３ｍｏｌ／Ｌの塩
酸溶液に塩化銅（Ｉ）を３ｍｏｌ／Ｌ〜５ｍｏｌ／Ｌ溶
解させた。EXAMPLE Carbonization treatment was carried out in a nitrogen stream using a styrene strongly acidic cation exchange resin obtained by sulfonating a styrene / divinylbenzene copolymer. In the carbonization treatment, the temperature was increased at a rate of 5 ° C./min, raised to 800 ° C., and maintained at that temperature for 60 minutes. The carbide obtained by performing the carbonization treatment was washed with water and dried, and the dried carbide was activated in a mixed gas stream of carbon dioxide and nitrogen to produce activated carbon. In the activation treatment, the temperature was increased at a rate of 5 ° C./min, raised to 900 ° C., and maintained at that temperature for 60 minutes. The activated carbon obtained by the activation treatment is washed with water and dried, immersed and impregnated with a copper (I) chloride solution dissolved in hydrochloric acid in a nitrogen atmosphere, and the impregnated activated carbon is dried to carry a copper compound-supported monoxide. A carbon adsorbent was obtained. The copper (I) chloride solution was prepared by dissolving copper (I) chloride at 3 mol / L to 5 mol / L in a 3 mol / L hydrochloric acid solution.
【００１４】前記本発明の製造方法で製造した一酸化炭
素吸着剤と従来のヤシ殻から製造した活性炭を用いた一
酸化炭素吸着剤について耐摩擦強度を測定した結果、前
者は０．０７５、後者は０．７６９であり、本発明の一
酸化炭素吸着剤の耐摩擦度は従来の約１０倍であり、極
めて粉化しにくいことが判明した。なお、耐摩擦強度
は、粒径が２５０〜３００μｍ以上の試料１０ｇを２５
０μｍフルイに採取し、１０円硬貨大の銅板を５枚入
れ、振動機で１５分間振動させ、受け皿に落ちた試料の
重量を測定して、次式により算出した。 耐摩擦強度＝（受け皿に落ちた試料の重量／１０）Ｘ１
００[0014] The friction resistance of the carbon monoxide adsorbent produced by the production method of the present invention and the carbon monoxide adsorbent using activated carbon produced from the conventional coconut shell was measured. Was 0.769, and the rub resistance of the carbon monoxide adsorbent of the present invention was about 10 times that of the conventional carbon monoxide adsorbent. In addition, the abrasion resistance was determined by measuring 10 g of a sample having a particle size of 250 to 300 μm or more by 25 g.
The sample was collected in a 0 μm sieve, and five copper plates of 10-yen coin size were placed, vibrated by a vibrator for 15 minutes, and the weight of the sample dropped on the pan was measured and calculated by the following equation. Friction resistance = (weight of sample dropped on saucer / 10) × 1
00
【００１５】また、前記本発明の製造方法で製造した一
酸化炭素吸着剤と従来のヤシ殻から製造した活性炭を用
いた一酸化炭素吸着剤について耐圧強度を測定した結
果、前者は２７．４６ｋｇ／ｍｍ2、後者は０．５１ｋ
ｇ／ｍｍ2であり、本発明の一酸化炭素吸着剤の耐圧強
度は従来の約５４倍であり、極めて強度が高く破砕しに
くいことが判明した。なお、耐圧強度は、木屋式硬度計
を用いて測定した。The pressure resistance of the carbon monoxide adsorbent produced by the production method of the present invention and the carbon monoxide adsorbent using activated carbon produced from a conventional coconut shell was measured. mm2, the latter is 0.51k
g / mm 2, and the pressure resistance of the carbon monoxide adsorbent of the present invention was about 54 times that of the conventional carbon monoxide adsorbent. The pressure resistance was measured using a Kiya hardness meter.
【００１６】また、前記本発明の製造方法で製造した一
酸化炭素吸着剤と従来のヤシ殻から製造した活性炭を用
いた一酸化炭素吸着剤について一酸化炭素吸着能を測定
した結果、一酸化炭素分圧が０．１ＭＰａ、温度が２０
℃のときに、前者は４．１２ｍ−ｍｏｌ（ＣＯ）／ｇ
（吸着剤）、後者は３．２１ｍ−ｍｏｌ（ＣＯ）／ｇ
（吸着剤）であり、本発明の一酸化炭素吸着剤の一酸化
炭素吸着能は従来の約１．２倍の吸着量が得られること
が判明した。（図１）なお、一酸化炭素吸着能は、磁気
浮遊式天秤で測定した。Further, the carbon monoxide adsorption capacity of the carbon monoxide adsorbent produced by the production method of the present invention and the carbon monoxide adsorbent using activated carbon produced from a conventional coconut shell were measured. Partial pressure 0.1 MPa, temperature 20
At ℃, the former is 4.12 m-mol (CO) / g
(Adsorbent), the latter is 3.21 m-mol (CO) / g
(Adsorbent), and it has been found that the carbon monoxide adsorbent of the present invention has an adsorption capacity of about 1.2 times that of the conventional carbon monoxide adsorbent. (FIG. 1) The ability to adsorb carbon monoxide was measured using a magnetic suspension balance.
【００１７】[0017]
【発明の効果】一酸化炭素吸着剤において、耐摩擦強度
及び耐圧強度が高いため、極めて摩耗及び粉化しにく
く、また、一酸化炭素吸着能の高い一酸化炭素吸着剤と
その一酸化炭素吸着剤を製造する方法である。As described above, the carbon monoxide adsorbent has a high friction resistance and a high pressure resistance, so that it is extremely hard to be worn and pulverized. It is a method of manufacturing.
【図１】本発明の一酸化炭素吸着剤と従来の一酸化炭素
吸着剤との一酸化炭素吸着能を比較した吸着等温線ク゛ラフFIG. 1 is an adsorption isotherm graph comparing the carbon monoxide adsorption capacity of a carbon monoxide adsorbent of the present invention and a conventional carbon monoxide adsorbent.
１：従来の一酸化炭素吸着剤 ２：本発明の一酸化炭素吸着剤 1: Conventional carbon monoxide adsorbent 2: Carbon monoxide adsorbent of the present invention
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G046 HA03 HB02 HB07 HC10 HC12 HC14 4G066 AA05B AA10D AA11B AA32B AA43D AC14A AE10A BA35 BA36 CA35 DA05 FA12 FA18 FA23 FA34 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G046 HA03 HB02 HB07 HC10 HC12 HC14 4G066 AA05B AA10D AA11B AA32B AA43D AC14A AE10A BA35 BA36 CA35 DA05 FA12 FA18 FA23 FA34
Claims (2)
なくとも銅化合物を担持したことを特徴とする一酸化炭
素吸着剤。1. An adsorbent for carbon monoxide, wherein at least a copper compound is supported on activated carbon produced from an ion exchange resin.
０〜１０００℃に加熱して炭化処理し、炭化処理して得
られた炭化物を二酸化炭素と窒素の雰囲気で７００〜１
０００℃に加熱して賦活処理して活性炭を製造し、その
活性炭に少なくとも銅化合物溶液を含浸し、その含浸活
性炭を乾燥して少なくとも銅化合物を担持した一酸化炭
素吸着剤を得ることを特徴とする一酸化炭素吸着剤の製
造方法。2. The method according to claim 1, wherein the ion exchange resin is in an inert gas atmosphere.
The carbonized material is heated at 0 to 1000 ° C. and carbonized, and the carbonized material obtained is carbonized at 700 to 1 in an atmosphere of carbon dioxide and nitrogen.
Activated carbon is produced by heating at 000 ° C. to perform an activation treatment, the activated carbon is impregnated with at least a copper compound solution, and the impregnated activated carbon is dried to obtain a carbon monoxide adsorbent carrying at least a copper compound. For producing a carbon monoxide adsorbent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000312780A JP2002119851A (en) | 2000-10-13 | 2000-10-13 | Carbon monoxide adsorbent and method of manufacturing for the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000312780A JP2002119851A (en) | 2000-10-13 | 2000-10-13 | Carbon monoxide adsorbent and method of manufacturing for the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002119851A true JP2002119851A (en) | 2002-04-23 |
Family
ID=18792302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005349303A (en) * | 2004-06-10 | 2005-12-22 | Kuraray Co Ltd | Carbon monoxide absorbing solid and its manufacturing method |
| JP2006131461A (en) * | 2004-11-08 | 2006-05-25 | Japan Organo Co Ltd | Activated carbon, its manufacturing method, and renal disease therapeutic drug |
| JP2011147895A (en) * | 2010-01-22 | 2011-08-04 | Tohoku Electric Power Co Inc | Method for manufacturing of adsorbent for nitrogen monoxide |
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| JP2000093798A (en) * | 1998-09-25 | 2000-04-04 | Mitsui Eng & Shipbuild Co Ltd | Catalyst for decomposing organic chlorine compound, its production, and method for treating exhaust gas |
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| JP2000093798A (en) * | 1998-09-25 | 2000-04-04 | Mitsui Eng & Shipbuild Co Ltd | Catalyst for decomposing organic chlorine compound, its production, and method for treating exhaust gas |
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| JP2005349303A (en) * | 2004-06-10 | 2005-12-22 | Kuraray Co Ltd | Carbon monoxide absorbing solid and its manufacturing method |
| JP4628698B2 (en) * | 2004-06-10 | 2011-02-09 | 株式会社クラレ | Carbon monoxide-absorbing solid and method for producing the same |
| JP2006131461A (en) * | 2004-11-08 | 2006-05-25 | Japan Organo Co Ltd | Activated carbon, its manufacturing method, and renal disease therapeutic drug |
| JP4693030B2 (en) * | 2004-11-08 | 2011-06-01 | オルガノ株式会社 | Method for producing activated carbon |
| JP2011147895A (en) * | 2010-01-22 | 2011-08-04 | Tohoku Electric Power Co Inc | Method for manufacturing of adsorbent for nitrogen monoxide |
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