JPH0732856B2 - Carbon dioxide adsorption separation method - Google Patents
Carbon dioxide adsorption separation methodInfo
- Publication number
- JPH0732856B2 JPH0732856B2 JP60178600A JP17860085A JPH0732856B2 JP H0732856 B2 JPH0732856 B2 JP H0732856B2 JP 60178600 A JP60178600 A JP 60178600A JP 17860085 A JP17860085 A JP 17860085A JP H0732856 B2 JPH0732856 B2 JP H0732856B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon dioxide
- adsorbent
- adsorption
- amount
- adsorbed
- 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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 189
- 239000001569 carbon dioxide Substances 0.000 title claims description 94
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 94
- 238000001179 sorption measurement Methods 0.000 title description 27
- 238000000926 separation method Methods 0.000 title description 10
- 239000003463 adsorbent Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 26
- 239000006229 carbon black Substances 0.000 claims description 25
- 150000001412 amines Chemical class 0.000 claims description 22
- 239000007789 gas Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 229920002873 Polyethylenimine Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 235000002597 Solanum melongena Nutrition 0.000 description 5
- 244000061458 Solanum melongena Species 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- 239000006231 channel black Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Landscapes
- Separation Of Gases By Adsorption (AREA)
- Carbon And Carbon Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は二酸化炭素を含有する混合ガスから二酸化炭素
を吸着分離する方法に関する。The present invention relates to a method for adsorbing and separating carbon dioxide from a mixed gas containing carbon dioxide.
二酸化炭素は、尿素合成をはじめとして、鋳物向（鋳型
硬化助剤）や溶接向（溶接用不活性ガス）、ドライアイ
ス製造などに用いられ、工業的には、石灰石を強熱する
か、または石炭などを燃焼させて製造される。Carbon dioxide is used for synthesizing urea, casting (mold hardening aid), welding (inert gas for welding), dry ice production, etc. Industrially, it heats limestone or It is manufactured by burning coal.
二酸化炭素の分離精製は炭酸ナトリウムなどの炭酸塩や
エタノールアミンなどのアミン類の冷水溶液に吸収させ
たのち加熱して回収する方法が一般的であるが、これら
の分離精製法は、回収した二酸化炭素中に水分が混入す
ることが不可避であり、液体吸収剤を用いるためにプロ
セス上の制約を受けるなどの短所を有する。In general, carbon dioxide is separated and purified by absorbing it in a cold aqueous solution of a carbonate such as sodium carbonate or amines such as ethanolamine and then heating it to recover it. It is unavoidable that water is mixed into carbon, and there are disadvantages such as restrictions on the process due to the use of the liquid absorbent.
最近注目されている二酸化炭素の大規模な用途として、
原油の増進回収（Enhanced Oil Recovery）があげられ
る。これは、二次回収の対象とする油層に二酸化炭素を
注入することにより、原油の粘度を低下させて原油回収
を行うものであり、ここでは、燃焼排ガスなどが二酸化
炭素源となるため、効率的な二酸化炭素分離技術の開発
が望まれる。As a large-scale application of carbon dioxide, which has recently received attention,
Enhanced oil recovery is an example. This is to reduce the viscosity of crude oil and recover crude oil by injecting carbon dioxide into the oil layer that is the target of secondary recovery. The development of effective carbon dioxide separation technology is desired.
一方、宇宙船、宇宙基地などの有人宇宙機器の生命維持
システムとして、人体から放出される二酸化炭素の除去
装置が不可欠であり、この二酸化炭素の分離除去には、
無重力下での取り扱いが容易な固体吸着剤が好適である
といわれる。On the other hand, as a life support system for manned space equipment such as spacecraft and space bases, a device for removing carbon dioxide released from the human body is indispensable.
It is said that a solid adsorbent that is easy to handle under zero gravity is suitable.
既に述べたエタノールアミンをはじめとして、アミン類
は二酸化炭素を選択的に吸収する性質を有しているの
で、アミン構造を持つ樹脂を用いれば二酸化炭素の吸着
分離は原理的に可能であるが、該樹脂に吸着剤としての
機能を賦与するためには、該樹脂を多孔体あるは微粒子
化して接ガス面積を十分に大きくする必要があつた。し
かしながら、通常、多孔質の樹脂を合成するには懸濁重
合法のような特殊な重合法が採用されるが、この方法で
はスチレン−ジビニルベンゼン共重合体など、適用可能
な樹脂が限定されるし、一方樹脂を微粒子化するには、
粉砕に多大な機械的エネルギーを必要とするという問題
があつた。Starting with ethanolamine, which has already been described, amines have a property of selectively absorbing carbon dioxide. Therefore, if a resin having an amine structure is used, carbon dioxide can be adsorbed and separated, in principle, In order to impart a function as an adsorbent to the resin, it was necessary to make the resin into a porous body or fine particles to sufficiently increase the gas contact area. However, usually, a special polymerization method such as a suspension polymerization method is adopted to synthesize a porous resin, but in this method, applicable resins such as a styrene-divinylbenzene copolymer are limited. On the other hand, in order to atomize the resin,
There has been a problem that crushing requires a large amount of mechanical energy.
そこで本発明者らは、上記とは全く発想を変えることに
より、アミン構造を持つ物質を用いた二酸化炭素の吸着
分離法を開発せんと意図したのである。Therefore, the present inventors intend to develop a method for adsorptive separation of carbon dioxide using a substance having an amine structure by completely changing the idea.
発明者らは、前述の、アミン構造を持つ樹脂に接ガス面
積が大きくなるような幾何学的状を与えた吸着剤とは全
く異なる吸着剤を鋭意探索した結果、カーボンブラツク
の粒子表面にアミン類が結合または吸着させて得た粉体
が二酸化炭素の吸着分離に極めて有効であることを見出
し、本発明の完成に至つた。すなわち、本発明は、アミ
ン類を結合または吸着させたカーボンブラツクを吸着剤
として用いることを特徴とする、混合ガスから二酸化炭
素を分離する新規な、方法に関する。The inventors of the present invention have intensively searched for an adsorbent which is completely different from the adsorbent in which a resin having an amine structure is given a geometric shape such that the gas contact area becomes large, and as a result, the amine on the surface of carbon black particles is It was found that the powder obtained by binding or adsorbing the compounds is extremely effective for the adsorption separation of carbon dioxide, and has completed the present invention. That is, the present invention relates to a novel method for separating carbon dioxide from a mixed gas, which is characterized by using a carbon black to which amines are bound or adsorbed as an adsorbent.
本発明の吸着分離法に用いられる吸着剤は、カーボンブ
ラツクにアミン類を結合または吸着させて得た粉体、ま
たは、該粉体を圧縮などの方法で任意の形状に成型した
ものであり、該吸着剤の二酸化炭素吸着能は、アミン類
を粉体であるカーボンブラツクの表面に導入し、接ガス
面積の大きな固体としたことに起因するものである。The adsorbent used in the adsorptive separation method of the present invention is a powder obtained by binding or adsorbing amines to carbon black, or the powder is molded into an arbitrary shape by a method such as compression, The carbon dioxide adsorbing ability of the adsorbent is due to the fact that amines were introduced into the surface of carbon black, which is powder, to form a solid having a large gas contact area.
カーボンブラツクは、その製造法により、フアーネスブ
ラツク、チヤンネルブラツク、ランプブラツク、サーマ
ルブラツク、アセチレンブラツクなどに分類されるが、
本発明の二酸化炭素吸着剤の調製には、いずれのカーボ
ンブラツクも使用できる。一方、本発明の二酸化炭素吸
着剤の調製に用いるアミン類とは１級、２級または３級
のアミン構造を有する有機化合物を意味する。また、カ
ーボンブラツクに結合させるべきアミン類はカーボンブ
ラツクとの結合に必要な、たとえば、１級または２級ア
ミン構造などの原子団を有している必要がある。Carbon black is classified into fannes black, channel black, lamp black, thermal black, acetylene black, etc. according to its manufacturing method.
Any carbon black can be used to prepare the carbon dioxide adsorbent of the present invention. On the other hand, the amines used for the preparation of the carbon dioxide adsorbent of the present invention mean organic compounds having a primary, secondary or tertiary amine structure. Further, the amines to be bonded to the carbon black must have an atomic group such as a primary or secondary amine structure necessary for bonding with the carbon black.
カーボンブラツクにアミン類を結合させる方法として
は、たとえば、カーボンブラツク粒子表面に存在する−
COOH基または硝酸酸化などの方法によつて該粒子表面に
導入した−COOH基をトリエチルアミンと反応させて−CO
O-〔NH（C2H5）３〕＋基とし、これをクロルぎ酸エチル
と反応させて−COOCOOC2H5基に変え、さらに、これをア
ジ化ナトリウムと反応させて−CON3基に変えたのち、１
級または２級のアミン構造を有するアミン類を反応させ
て結合させる方法、カーボンブラツク粒子表面の−COOH
基に１級または２級のアミン構造を有するアミン類を直
接反応させて結合させる方法、などがある。一方、カー
ボンブラツクにアミン類を吸着させる方法としては、た
とえば、カーボンブラツクと任意のアミン類をメタノー
ル、エタノール、ジメチルスルホキシドなどの溶媒中で
混合する方法、カーボンブラツクと任意の液体アミン類
を直接混合する方法、などがある。As a method for binding amines to carbon black, for example, the method of existing on the surface of carbon black particles is used.
-COOH group introduced by a method such as COOH group or nitric acid oxidation with triethylamine to react with -COOH group
O - [NH (C 2 H 5) 3] as a + group, which is reacted with chloroformate ethyl changed to -COOCOOC 2 H 5 group, further, which is reacted with sodium azide -CON 3 group After changing to
Method of reacting and binding amines having a secondary or secondary amine structure, -COOH on the surface of carbon black particles
There is a method in which an amine having a primary or secondary amine structure is directly reacted with the group to bond it. On the other hand, as a method of adsorbing amines to carbon black, for example, a method of mixing carbon black and arbitrary amines in a solvent such as methanol, ethanol, or dimethyl sulfoxide, a method of directly mixing carbon black and arbitrary liquid amines How to do, etc.
本発明の吸着分離法に用いられる吸着剤の組成について
述べると、アミン類のカーボンブラツクに対する重量比
は0.1〜10、好ましくは0.5〜２である。The composition of the adsorbent used in the adsorption separation method of the present invention will be described. The weight ratio of amines to carbon black is 0.1 to 10, preferably 0.5 to 2.
本発明の、アミン類を結合または吸着させたカーボンブ
ラツクは、常温、常圧下で二酸化炭素を吸着し、液圧す
るか、二酸化炭素分圧を下げるか、あるいは、加熱する
ことにより、吸着された二酸化炭素を放出させることが
できるので、混合ガスから二酸化炭素を容易に分離する
ことが可能である。The carbon black bound or adsorbed with amines of the present invention adsorbs carbon dioxide at room temperature and atmospheric pressure, and the carbon dioxide adsorbed by applying liquid pressure, lowering the carbon dioxide partial pressure, or heating. Since carbon can be released, carbon dioxide can be easily separated from the mixed gas.
次に、本発明を実施例によつてさらに説明する。Next, the present invention will be further described with reference to examples.
実施例１ 本発明の吸着分離法に用いる吸着剤を次のように調製し
た。まず、コロンビアンカーボン社Columbian Carbon C
o.製のカーボンブラツク（チヤンネルブラツク）ネオス
ペクトラII（比表面積906m2/g、−COOH含有量0.4mmol/
g）5.0gを、5mmHgの減圧下、120℃において十分に乾燥
させたのち、テトラヒドロフラン50mlと混合し、０℃に
冷却した。この混合物に、トリエチルアミン0.4g（0.4
×10-2mol）をテトラヒドロフラン10mlに溶解させた溶
液を加え、０℃において３時間かくはんしながら反応さ
せたのち、−10℃に冷却し、さらに、クロルぎ酸エチル
0.45g（0.4×10-2mol）をテトラヒドロフラン10mlに溶
解させた溶液を加え、−10℃において10時間かくはんし
ながら反応させたのち、この混合物の温度を０℃とし
た。その後、この混合物に、アジ化ナトリウム1.3g（0.
02mol）を少量の純水に溶解させて加え、０℃において1
0時間かくはんしながら反応させた。反応後、生成物を
過し、冷水で数回洗浄したのち、冷メタノールで洗浄
した残渣を5mmHgの減圧下、室温で乾燥させて、粒子表
面の−COOH基を−CON3基に変えたカーボンブラツクを得
た。次いで、このカーボンブラツク1.5gと日本触媒化学
工業（株）製のポリエチレンイミン（平均分子量約3000
0）20gとをジメチルスルホキシド30mlに加え、80℃にお
いて24時間かくはんしながら反応させたのち、メタノー
ルを溶媒として100時間のソツクスレー抽出を行い、カ
ーボンブラツクに結合していないポリエチレンイミンを
除去し、5mmHgの減圧下、120℃において十分に乾燥させ
て、2.90gの二酸化炭素吸着剤（カーボンブラツク1gあ
たりのポリエチレンイミンの結合量0.93g）を得た。Example 1 An adsorbent used in the adsorption separation method of the present invention was prepared as follows. First, Columbian Carbon C
Carbon black (Channel black) Neo Spectra II (specific surface area 906 m 2 / g, -COOH content 0.4 mmol /
g) 5.0 g was sufficiently dried at 120 ° C. under a reduced pressure of 5 mmHg, then mixed with 50 ml of tetrahydrofuran, and cooled to 0 ° C. To this mixture, 0.4 g of triethylamine (0.4
X10 -2 mol) in 10 ml of tetrahydrofuran was added, and the mixture was reacted at 0 ° C with stirring for 3 hours, cooled to -10 ° C, and further added with ethyl chloroformate.
A solution prepared by dissolving 0.45 g (0.4 × 10 -2 mol) in 10 ml of tetrahydrofuran was added, and the reaction was carried out while stirring at -10 ° C for 10 hours, and then the temperature of this mixture was adjusted to 0 ° C. Then 1.3 g of sodium azide (0.
02mol) dissolved in a small amount of pure water and added,
The reaction was allowed to stir for 0 hours. After the reaction, the product was passed, washed with cold water several times, and then the residue washed with cold methanol was dried at room temperature under a reduced pressure of 5 mmHg, and the -COOH group on the particle surface was changed to a -CON 3 group. I got a black. Next, 1.5 g of this carbon black and polyethyleneimine (average molecular weight of about 3000
0) 20g was added to 30ml of dimethylsulfoxide and reacted at 80 ° C for 24 hours with stirring, and then Soxhlet extraction was carried out for 100 hours using methanol as a solvent to remove polyethyleneimine not bound to carbon black, and 5mmHg Sufficiently dried under reduced pressure at 120 ° C. to obtain 2.90 g of carbon dioxide adsorbent (bound amount of polyethyleneimine of 0.93 g per 1 g of carbon black).
上記の二酸化炭素吸着剤2.0gを内容積100mlのなす形フ
ラスコに入れ、再度、5mmHgの減圧下で排気しながら120
℃に１時間保つたのち、減圧下で室温になるまで放置し
た。次いで、このなす形フラスコを1atmの二酸化炭素３
を入れた容器と結合し、室温で二酸化炭素を該吸着剤
と接触させ、二酸化炭素吸着量をガスビユーレツト法に
より測定した。2.0 g of the above carbon dioxide adsorbent was placed in an eggplant-shaped flask having an internal volume of 100 ml, and again while evacuating under a reduced pressure of 5 mmHg, 120
After keeping the temperature at 0 ° C. for 1 hour, the mixture was left under reduced pressure until it reached room temperature. The eggplant-shaped flask is then placed in 1 atm of carbon dioxide 3
It was connected to a container containing the adsorbent, carbon dioxide was brought into contact with the adsorbent at room temperature, and the amount of adsorbed carbon dioxide was measured by the gas view method.
二酸化炭素の吸着はすみやかに始まり、10分後には1.65
m molの二酸化炭素が吸着され60分後の二酸化炭素吸着
量は4.30n molに達した。The adsorption of carbon dioxide starts quickly, and after 10 minutes is 1.65.
The amount of carbon dioxide adsorbed 60 minutes after the adsorption of m mol carbon dioxide reached 4.30 nmol.
次に、真空ポンプを用いて、この二酸化炭素吸着剤の入
つたなす形フラスコ内を、室温において、5mmHgの減圧
下で20分間排気して、吸着された二酸化炭素を放出させ
たのち、このなす形フラスコを1atmの二酸化炭素３を
入れた容器と結合し、室温で、二酸化炭素を吸着剤と接
触させた。Next, using a vacuum pump, the inside of the eggplant shaped flask containing the carbon dioxide adsorbent was evacuated at room temperature under a reduced pressure of 5 mmHg for 20 minutes to release the adsorbed carbon dioxide, and then this eggplant The shaped flask was combined with a vessel containing 1 atm of carbon dioxide 3 and carbon dioxide was contacted with the adsorbent at room temperature.
二酸化炭素の吸着はすみやかに始まり、10分後には1.60
m molの二酸化炭素が吸着され、60分後の二酸化炭素吸
着量は4.19m molに達した。The adsorption of carbon dioxide starts quickly and after 10 minutes is 1.60.
After adsorbing 60 mol of carbon dioxide, the amount of adsorbed carbon dioxide reached 4.19 mmol after 60 minutes.
以後、上記の操作を繰り返しても、二酸化炭素の吸着速
度および吸着量に変化は見られなかつた。After that, no change was observed in the adsorption rate and the adsorption amount of carbon dioxide even if the above operation was repeated.
実施例２ 実施例１と同様に調製した二酸化炭素吸着剤2.0gを内容
積100mlのなす形フラスコに入れ、5mmHgの減圧下で排気
しながら120℃に１時間保つたのち、減圧下で室温にな
るまで放置した。次いで、このなす形フラスコを1atmの
二酸化炭素３を入れた容器と結合し、室温で、二酸化
炭素を該吸着剤と接触させ、二酸化炭素吸着量をガスビ
ユーレツト法により測定した。Example 2 2.0 g of carbon dioxide adsorbent prepared in the same manner as in Example 1 was placed in an eggplant-shaped flask having an internal volume of 100 ml, and the mixture was kept at 120 ° C. for 1 hour while being evacuated under a reduced pressure of 5 mmHg. I left it until. Next, this eggplant-shaped flask was combined with a container containing 1 atm of carbon dioxide 3, and carbon dioxide was brought into contact with the adsorbent at room temperature, and the amount of carbon dioxide adsorbed was measured by a gas biuret method.
二酸化炭素の吸着はすみやかに始まり、10分後には1.65
m molの二酸化炭素が吸着され、60分後の二酸化炭素吸
着量は4.30m molに達した。The adsorption of carbon dioxide starts quickly, and after 10 minutes is 1.65.
After adsorbing m mol carbon dioxide, the amount of carbon dioxide adsorbed after 60 minutes reached 4.30 mmol.
次に、この吸着剤を1atmで120℃に加熱し二酸化炭素の
放出量をガスビユーレツト法により測定した。二酸化炭
素はすみやかに放出され、放出量は20分後に4.28m mol
に達した。放出ガスをガスクロマトグラフで分析した結
果、放出ガスは二酸化炭素のみであり、他の成分は検出
されなかつた。Next, this adsorbent was heated to 120 ° C. at 1 atm, and the amount of carbon dioxide released was measured by a gas view method. Carbon dioxide is released promptly, and the release amount is 4.28 mmol after 20 minutes.
Reached As a result of gas chromatograph analysis of the released gas, the released gas was only carbon dioxide, and other components were not detected.
その後、二酸化炭素を放出させた吸着剤の入つたなす形
フラスコを、窒素を通じながら放冷したのち、1atmの二
酸化炭素３を入れた容器と結合し、室温で、二酸化炭
素を吸着剤と接触させた。After that, the eggplant shaped flask containing the adsorbent from which carbon dioxide was released was allowed to cool while nitrogen was passed through, and then combined with the container containing 1 atm of carbon dioxide 3, and the carbon dioxide was brought into contact with the adsorbent at room temperature. It was
二酸化炭素の吸着はすみやかに始まり、10分後には1.65
m molの二酸化炭素が吸着され60分後の二酸化炭素吸着
量は4.29m molに達した。The adsorption of carbon dioxide starts quickly, and after 10 minutes is 1.65.
The amount of carbon dioxide adsorbed 60 minutes after the adsorption of m mol of carbon dioxide reached 4.29 mmol.
この吸着剤を1amtで120℃に加熱すると、二酸化炭素は
すみやかに放出され、放出量は20分後に4.29m molに達
した。When the adsorbent was heated to 120 ℃ at 1amt, carbon dioxide was released rapidly and the release amount reached 4.29mmol after 20 minutes.
以後、上記の操作を繰り返しても、二酸化炭素の吸着速
度および吸着量に変化は見られなかつた。After that, no change was observed in the adsorption rate and the adsorption amount of carbon dioxide even if the above operation was repeated.
実施例３ 本発明の吸着分離法に用いる吸着剤を次のように調製し
た。まず、実施例１と同様に十分乾燥させたカーボンブ
ラツクネオスペクトラII 1.5gと実施例１と同一のポリ
エチレンイミン20gとをジメチルスルホキシド30mlに加
え、80℃において24時間かくはんしたのち、メタノール
を溶媒として100時間のソツクスレー抽出を行い、カー
ボンブラツクに吸着していないポリエチレンイミンを除
去し、5mmHgの減圧下、120℃において十分に乾燥させ
て、2.85gの二酸化吸着剤（カーボンブラツク1gあたり
のポリエチレンイミン吸着量0.90g）を得た。Example 3 An adsorbent used in the adsorption separation method of the present invention was prepared as follows. First, in the same manner as in Example 1, 1.5 g of carbon black Neospectra II sufficiently dried and 20 g of the same polyethyleneimine as in Example 1 were added to 30 ml of dimethyl sulfoxide, and the mixture was stirred at 80 ° C. for 24 hours, and then methanol was used as a solvent. Soxhlet extraction for 100 hours is performed to remove polyethyleneimine that is not adsorbed on carbon black, and it is thoroughly dried at 120 ° C under a reduced pressure of 5 mmHg, and 2.85 g of a carbon dioxide adsorbent (polyethyleneimine adsorption per 1 g of carbon black is adsorbed An amount of 0.90 g) was obtained.
上記の二酸化炭素吸着剤2.0gを内容積100mlのなす形フ
ラスコに入れ、再度、5mmHgの減圧下で排気しながら120
℃に１時間保つたのち、減圧下で室温になるまで放置し
た。次いで、このなす形フラスコを1atmの二酸化炭素３
を入れた容器と結合し、室温で、二酸化炭素を該吸着
剤と接触させ、二酸化炭素吸着量をガスビユーレツト法
により測定した。2.0 g of the above carbon dioxide adsorbent was placed in an eggplant-shaped flask having an internal volume of 100 ml, and again while evacuating under a reduced pressure of 5 mmHg, 120
After keeping the temperature at 0 ° C. for 1 hour, the mixture was left under reduced pressure until it reached room temperature. The eggplant-shaped flask is then placed in 1 atm of carbon dioxide 3
It was combined with a container containing the adsorbent, carbon dioxide was brought into contact with the adsorbent at room temperature, and the amount of adsorbed carbon dioxide was measured by the gas view method.
二酸化炭素の吸着はすみやかに始まり、10分後には1.63
m molの二酸化炭素が吸着され60分後の二酸化炭素吸着
量は4.21m molに達した。The adsorption of carbon dioxide starts quickly and after 10 minutes 1.63
The amount of carbon dioxide adsorbed after 60 minutes reached 4.21 mmol after the adsorption of m mol carbon dioxide.
次に真空ポンプを用いて、この二酸化炭素吸着剤の入つ
たなす形フラスコ内を、室温において、5mmHgの減圧下
で20分間排気して、吸着された二酸化炭素を放出させた
のち、このなす形フラスコを1atmの二酸化炭素３を入
れた容器と結合し、室温で二酸化炭素を吸着剤と接触さ
せた。Next, using a vacuum pump, the inside of the eggplant shaped flask containing the carbon dioxide adsorbent was evacuated at room temperature under a reduced pressure of 5 mmHg for 20 minutes to release the adsorbed carbon dioxide, and then the eggplant shaped The flask was combined with a container containing 1 atm of carbon dioxide 3 and carbon dioxide was contacted with the adsorbent at room temperature.
二酸化炭素の吸着はすみやかに始まり、10分後には1.59
m molの二酸化炭素が吸着され、60分後の二酸化炭素吸
着量は4.08m molに達した。The adsorption of carbon dioxide begins quickly and after 10 minutes it is 1.59.
After adsorbing m mol of carbon dioxide, the amount of adsorbed carbon dioxide after 60 minutes reached 4.08 mmol.
以後、上記の操作を繰り返しても、二酸化炭素の吸着速
度および吸着量に変化は見られなかつた。After that, no change was observed in the adsorption rate and the adsorption amount of carbon dioxide even if the above operation was repeated.
実施例４ 実施例３と同様に調製した二酸化炭素吸着剤2.0gを内容
積100mlのなす形フラスコに入れ、5mmHgの減圧下で排気
しながら120℃に１時間保つたのち、減圧下で室温にな
るまで放置した。次いで、このなす形フラスコを1atmの
二酸化炭素３を入れた容器と結合し、室温で、二酸化
炭素を該吸着剤と接触させ、二酸化炭素吸着量をガスビ
ユーレツト法により測定した。Example 4 2.0 g of carbon dioxide adsorbent prepared in the same manner as in Example 3 was placed in a round-bottomed flask having an internal volume of 100 ml and kept at 120 ° C. for 1 hour while being evacuated under a reduced pressure of 5 mmHg, and then brought to room temperature under a reduced pressure. I left it until. Next, this eggplant-shaped flask was combined with a container containing 1 atm of carbon dioxide 3, and carbon dioxide was brought into contact with the adsorbent at room temperature, and the amount of carbon dioxide adsorbed was measured by a gas biuret method.
二酸化炭素の吸着はすみやかに始まり、10分後には1.62
m molの二酸化炭素が吸着され60分後の二酸化炭素吸着
量は4.22m molに達した。The adsorption of carbon dioxide starts quickly, and 1.62 after 10 minutes.
The amount of carbon dioxide adsorbed after 60 minutes reached 4.22 mMol after adsorbing m mol of carbon dioxide.
次に、この吸着剤を1atmで120℃に加熱し、二酸化炭素
の放出量をガスビユーレツト法により測定した。二酸化
炭素はすみやかに放出され、放出量は20分後に4.21m mo
lに達した。放出ガスをガスクロマトグラフで分析した
結果、放出ガスは二酸化炭素のみであり、他の成分は検
出されなかつた。Next, this adsorbent was heated to 120 ° C. at 1 atm, and the amount of carbon dioxide released was measured by a gas view method. Carbon dioxide is released promptly, and the amount released is 4.21m mo after 20 minutes.
has reached l. As a result of gas chromatograph analysis of the released gas, the released gas was only carbon dioxide, and other components were not detected.
その後、二酸化炭素を放出させた吸着剤の入つたなす形
フラスコを窒素を通じながら放冷したのち、1atmの二酸
化炭素３を入れた容器と結合し、室温で、二酸化炭素
を吸着剤と接触させた。After that, the eggplant-shaped flask containing the adsorbent from which carbon dioxide was released was allowed to cool while passing nitrogen through it, and then combined with a container containing 1 atm of carbon dioxide 3, and the carbon dioxide was brought into contact with the adsorbent at room temperature. .
二酸化炭素の吸着はすみやかに始まり、10分後には1.63
m molの二酸化炭素が吸着され、60分後の二酸化炭素吸
着量は4.21m molに達した。The adsorption of carbon dioxide starts quickly and after 10 minutes 1.63
After adsorbing 60 mol of carbon dioxide, the amount of adsorbed carbon dioxide reached 4.21 mmol after 60 minutes.
この吸着剤を1atmで120℃に加熱すると、二酸化炭素は
すみやかに放出され、放出量は20分後に4.21m molに達
した。When the adsorbent was heated to 120 ℃ at 1 atm, carbon dioxide was rapidly released, and the release amount reached 4.21 mmol after 20 minutes.
以後、上記の操作を繰り返しても、二酸化炭素の吸着速
度および吸着量に変化は見られなかつた。After that, no change was observed in the adsorption rate and the adsorption amount of carbon dioxide even if the above operation was repeated.
本発明は、実施例に記述した事実に基づく、全く新規
な、二酸化炭素の吸着分離法を提供するものである。The present invention provides a completely new method for adsorptive separation of carbon dioxide based on the facts described in the examples.
実施例の結果から明らかなように本発明の方法は常温常
圧下で二酸化炭素を吸着し、簡単な操作で吸着した二酸
化炭素を放出させることができるので、混合ガスから二
酸化炭素を容易に分離できるし、吸着・放出を繰り返し
ても性能低下のない優れた方法である。As is clear from the results of the examples, the method of the present invention can adsorb carbon dioxide at room temperature and atmospheric pressure and release the adsorbed carbon dioxide by a simple operation, so that carbon dioxide can be easily separated from the mixed gas. However, it is an excellent method that does not deteriorate in performance even after repeated adsorption / release.
エチレンジアミンなどの低分子量のアミン類と同様に、
実施例に記述したポリエチレンイミンも常温において液
体であるが、これらの液体アミン類も、カーボンブラツ
クに結合または吸着させることにより、接ガス面積の大
きな粉体としての取り扱いが可能となる。この点は本発
明の吸着分離法に用いられる吸着剤の大きな特徴であ
り、該吸着剤は、粉体としてのみならず、圧縮などの方
法で任意の形状に成型して使用することもできる。Like low molecular weight amines such as ethylenediamine,
Polyethyleneimine described in the examples is also a liquid at room temperature, but these liquid amines can be handled as a powder having a large gas contact area by binding or adsorbing to the carbon black. This point is a major feature of the adsorbent used in the adsorption separation method of the present invention, and the adsorbent can be used not only as a powder but also by molding into an arbitrary shape by a method such as compression.
Claims (1)
ブラツクを吸着剤として用いることを特徴とする、混合
ガスから二酸化炭素を分離する方法。1. A method for separating carbon dioxide from a mixed gas, which comprises using as an adsorbent a carbon black to which amines are bound or adsorbed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60178600A JPH0732856B2 (en) | 1985-08-15 | 1985-08-15 | Carbon dioxide adsorption separation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60178600A JPH0732856B2 (en) | 1985-08-15 | 1985-08-15 | Carbon dioxide adsorption separation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6241709A JPS6241709A (en) | 1987-02-23 |
| JPH0732856B2 true JPH0732856B2 (en) | 1995-04-12 |
Family
ID=16051286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60178600A Expired - Lifetime JPH0732856B2 (en) | 1985-08-15 | 1985-08-15 | Carbon dioxide adsorption separation method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0732856B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5876488A (en) * | 1996-10-22 | 1999-03-02 | United Technologies Corporation | Regenerable solid amine sorbent |
| US6787029B2 (en) | 2001-08-31 | 2004-09-07 | Cabot Corporation | Material for chromatography |
| CN105080493A (en) * | 2015-08-31 | 2015-11-25 | 保护伞环保科技成都有限公司 | Indoor formaldehyde-cleaning agent |
| CN118341406A (en) * | 2024-05-21 | 2024-07-16 | 中国矿业大学 | A highly stable solid amine CO2 adsorbent and its preparation method and application |
-
1985
- 1985-08-15 JP JP60178600A patent/JPH0732856B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6241709A (en) | 1987-02-23 |
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