JP6055134B1 - 二酸化炭素吸着剤及びその製造方法、並びに、二酸化炭素分離回収システム - Google Patents
二酸化炭素吸着剤及びその製造方法、並びに、二酸化炭素分離回収システム Download PDFInfo
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- JP6055134B1 JP6055134B1 JP2016049103A JP2016049103A JP6055134B1 JP 6055134 B1 JP6055134 B1 JP 6055134B1 JP 2016049103 A JP2016049103 A JP 2016049103A JP 2016049103 A JP2016049103 A JP 2016049103A JP 6055134 B1 JP6055134 B1 JP 6055134B1
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- Prior art keywords
- carbon dioxide
- silica gel
- adsorbent
- dioxide adsorbent
- tank
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 316
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 158
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 157
- 239000003463 adsorbent Substances 0.000 title claims abstract description 130
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 238000011084 recovery Methods 0.000 title claims description 18
- 238000000926 separation method Methods 0.000 title claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000000741 silica gel Substances 0.000 claims abstract description 88
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 88
- 239000011148 porous material Substances 0.000 claims abstract description 60
- 239000002245 particle Substances 0.000 claims abstract description 38
- -1 amine compound Chemical class 0.000 claims abstract description 35
- 238000001179 sorption measurement Methods 0.000 claims description 58
- 238000003795 desorption Methods 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 150000001412 amines Chemical class 0.000 claims description 29
- 229920000768 polyamine Polymers 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000005299 abrasion Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 44
- 238000001035 drying Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 17
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 9
- 229910052753 mercury Inorganic materials 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 8
- 239000003814 drug Substances 0.000 description 7
- 229940079593 drug Drugs 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000003672 processing method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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Abstract
Description
アミン化合物の濃度が5%以上70%以下、且つ、温度が10℃以上100℃以下のアミン水溶液を調製する工程と、
前記アミン水溶液にシリカゲルを含浸させる工程と、
前記アミン化合物を担持した前記シリカゲルを通気乾燥させる工程とを含み、
前記シリカゲルは、粒子径が1mm以上5mm以下であり、平均細孔径が10nm以上100nm以下であり、且つ、細孔容積が0.1cm3/g以上1.3cm3/g以下であることを特徴としている。但し、上記粒子径、細孔容積、及び平均細孔径は、いずれもアミン化合物が担持されていない状態のシリカゲルにおける値である。
N=(W/W0)×100…(1)
(但し、N:シリカゲルの耐水性[%]、W0:水に浸漬したシリカゲルの粒子の全個数[個]、W:W0のうち割れの発生しなかったものの個数[個])
図1では、二酸化炭素吸着剤が使用され得る二酸化炭素分離回収システム1の概略構成が示されている。図1に示す二酸化炭素分離回収システム1は、吸着剤を用いて被処理ガスに含まれる二酸化炭素を選択的に分離する二酸化炭素分離システム1Aと、吸着剤から二酸化炭素を脱着(脱離)して回収する二酸化炭素回収システム1Bとが複合された連続処理方式のシステムである。
上記二酸化炭素分離回収システム1で使用される吸着剤(二酸化炭素吸着剤)は、シリカゲルにアミン化合物を担持させて成るものである。
(1)黒色フェルト上に100粒以上のシリカゲル試料を、なるべく粒子同士が接触しないように並べる。
(2)シリカゲル試料の粒子を100mm×140mmの範囲視野で撮影する。
(3)画像処理ソフトウェアImageJ(アメリカ国立衛生研究所NIH)を用いて、撮影した画像を二値化し、各粒子の面積を求める。
(4)粒子が真球であると仮定し、求めた各粒子の面積から粒子径を求める。
なお、求めた粒子径から、個数平均径(=Σ(粒子径)/(評価した粒子の数))を求め、この個数平均径を粒子径として用いてもよい。
上記の吸着剤は、以下に説明する方法で製造することができる。
N=(W/W0)×100…(1)
但し、 N:シリカゲルの耐水性[%]
W0:水に浸漬したシリカゲルの粒子の全個数[個]
W:W0のうち割れの発生しなかったものの個数[個]
以下(1)〜(5)の手順で二酸化炭素吸着剤の試料を作製した。
(1)基材(シリカゲル)を約300mL採取し、重量(W)を測定する。
(2)薬剤(アミン化合物)を所定の担持溶液濃度(%)に希釈し、瓶に入れる。
(3)(1)の基材を(2)の瓶に入れ、室温で8時間以上放置する。ここで、基材と薬剤の重量比が1:3となるようにした。
(4)(3)から基材を取り出し、遠心分離(1100rpm)を行う。
(5)容器に充填し、乾燥ガス(40℃,15L/minの窒素ガス)を流して、薬剤を担持した基材を通気乾燥させる。なお、薬剤を担持した基材を乾燥する乾燥槽の出口のガス温度が安定した時点より2時間経過後を、薬剤を担持した基材(即ち、二酸化炭素吸着剤)の乾燥終了条件とした。
(1)内径25mmの吸着槽に300mmの高さまで試料を固く充填する。ここで、充填された試料は147mLであった。
(2)吸着ガスをバイパスラインに流し、濃度が10.0%であることを確認する。ここで、吸着ガスは、10体積%の二酸化炭素を含み、湿度が湿度5%RH以下、且つ、25℃の空気である。また、吸着ガスの空塔速度は0.05m/sとする。
(3)吸着ガスを吸着槽へ流し、吸着槽の出口のガス濃度を測定する。
(4)出口ガス濃度が10.0%になったこと(即ち、飽和吸着となったこと)を確認し、吸着工程を終了する。
Claims (7)
- 被処理ガスに含まれる二酸化炭素を二酸化炭素吸着剤へ吸着させる吸着槽と、二酸化炭素を吸着した前記二酸化炭素吸着剤に脱着用水蒸気を凝縮させることにより前記二酸化炭素吸着剤から二酸化炭素を脱着させる脱着槽とを備えた二酸化炭素分離回収システムにおいて、前記吸着槽及び前記脱着槽において移動層を形成する、シリカゲルにアミン化合物を担持させて成る二酸化炭素吸着剤であって、
前記シリカゲルは、粒子径が1mm以上5mm以下であり、平均細孔径が10nm以上100nm以下であり、且つ、細孔容積が0.1cm3/g以上1.3cm3/g以下である、
二酸化炭素吸着剤。 - 前記シリカゲルは、次式(1)で定義される耐水性Nが45%以上である、
N=(W/W0)×100…(1)
(但し、N:シリカゲルの耐水性[%]、W0:水に浸漬したシリカゲルの粒子の全個数[個]、W:W0のうち割れの発生しなかったものの個数[個])
請求項1に記載の二酸化炭素吸着剤。 - 前記アミン化合物が、少なくとも1つのヒドロキシル基を有するアミン類、及びポリアミン類の少なくとも一方を含む、
請求項1又は2に記載の二酸化炭素吸着剤。 - 被処理ガスに含まれる二酸化炭素を二酸化炭素吸着剤へ吸着させる吸着槽と、二酸化炭素を吸着した前記二酸化炭素吸着剤に脱着用水蒸気を凝縮させることにより前記二酸化炭素吸着剤から二酸化炭素を脱着させる脱着槽とを備えた二酸化炭素分離回収システムにおいて、前記吸着槽及び前記脱着槽において移動層を形成する二酸化炭素吸着剤の製造方法であって、
アミン化合物の濃度が5%以上70%以下、且つ、温度が10℃以上100℃以下のアミン水溶液を調製する工程と、
前記アミン水溶液にシリカゲルを含浸させる工程と、
前記アミン化合物を担持した前記シリカゲルを通気乾燥させる工程とを含み、
前記シリカゲルは、粒子径が1mm以上5mm以下であり、平均細孔径が10nm以上100nm以下であり、且つ、細孔容積が0.1cm3/g以上1.3cm3/g以下である、
二酸化炭素吸着剤の製造方法。 - 前記シリカゲルは、次式(1)で定義される耐水性Nが45%以上である、
N=(W/W0)×100…(1)
(但し、N:シリカゲルの耐水性[%]、W0:水に浸漬したシリカゲルの粒子の全個数[個]、W:W0のうち割れの発生しなかったものの個数[個])
請求項4に記載の二酸化炭素吸着剤の製造方法。 - 前記アミン化合物が、少なくとも1つのヒドロキシル基を有するアミン類、及びポリアミン類の少なくとも一方を含む、
請求項4又は5に記載の二酸化炭素吸着剤の製造方法。 - 請求項1〜3のいずれか一項に記載の二酸化炭素吸着剤により内部に移動層が形成された吸着槽及び脱着槽を備え、
前記吸着槽の下部に二酸化炭素を含む被処理ガスが供給される被処理ガス供給口が設けられ、前記吸着槽の上部に前記二酸化炭素が前記二酸化炭素吸着剤に吸着除去されたオフガスを排出するオフガス排出口が設けられており、
前記脱着槽の下部に脱着用水蒸気が供給される水蒸気供給口が設けられ、前記脱着槽の上部に前記二酸化炭素吸着剤から脱離した二酸化炭素を排出する二酸化炭素排出口が設けられている、二酸化炭素分離回収システム。
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US11185842B2 (en) | 2021-11-30 |
US20190126235A1 (en) | 2019-05-02 |
AU2017232470B2 (en) | 2020-04-02 |
US11529608B2 (en) | 2022-12-20 |
WO2017159663A1 (ja) | 2017-09-21 |
CN108778489B (zh) | 2021-08-03 |
JP2017164656A (ja) | 2017-09-21 |
AU2017232470A1 (en) | 2018-11-08 |
CN108778489A (zh) | 2018-11-09 |
US20220040667A1 (en) | 2022-02-10 |
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