JP2015515925A - 二酸化炭素を捕獲および封鎖するためのシステムおよび方法 - Google Patents
二酸化炭素を捕獲および封鎖するためのシステムおよび方法 Download PDFInfo
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- JP2015515925A JP2015515925A JP2015510489A JP2015510489A JP2015515925A JP 2015515925 A JP2015515925 A JP 2015515925A JP 2015510489 A JP2015510489 A JP 2015510489A JP 2015510489 A JP2015510489 A JP 2015510489A JP 2015515925 A JP2015515925 A JP 2015515925A
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- carbon dioxide
- adsorbent
- air
- water vapor
- capture
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- B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
- B01D2259/40043—Purging
- B01D2259/4005—Nature of purge gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/402—Further details for adsorption processes and devices using two beds
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- 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
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- 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
Abstract
Description
CE/MMBTU=100万BTUあたりのエネルギーのコスト、すなわち1.055×109ジュール×1/CE
E/T=MMBTUで測定された1トンのCO2あたりの必要なエネルギー
CO2/MMBTU=100万BTUあたりの放出されたCO2の量
REV=1トンのCO2あたりの財源
[0035]システムの稼働費をコンピュータで算出する場合、ボイラーおよび発電の資本コストは無視するものとし、燃料によって生成したCO2にかかる余分な資本費用はなく、燃料にかかるコストのみが発生するものと仮定する。SH/HR=1.2のケースと仮定すると、これは、CE/T=4×3−40×4×0.053=1トンあたり3.50ドルとなるように、E/T=4MMBTU、およびREV=天然ガス1トンあたり40.00ドル、CE/MMBTU=3.00ドル;CO2/MMBTU=53kgと解釈される。
同時係属中の出願(米国特許公報第2011/0296872号)で示されているシステムに従って、以下の本発明の好ましい実施態様は、より高度に濃縮されたCO2のガス混合物の処理を可能にすることが見出されている。本明細書で説明されるプロセスに従って、基板がこの説明に記載された必要条件を確実に満たすことにより、例えば発電所からの温室効果ガスを完全に大気から除去するだけでなく、本発明のプロセスにより正味で炭素マイナスな作用を起こし、工場排気よりも多くのCO2を大気から引き出して、結果的に大気中のCO2も総体的に低減させるように、濃縮されたCO2混合物を効率的且つ低コストでうまく処理できる。
[0051]商品化しようとする本発明を取り入れたシステムの構造の設計において、以下の設計パラメーターが考慮されると予想される。一般的には、基板で吸着剤部位の含有量を増加させたら、CO2と結合するのに利用可能なアミン部位の存在比で定義されるような高いアミン効率も要求される。これが、第一アミンが好ましい理由であり、さらに過量の吸着剤による孔の目詰まりが最小化されるように含有量を調節することの理由でもある。実験結果から、アミン効率と含有量の増加とのバランスをとった最適な含有量は、有機アミンが結合するかまたはその孔表面上に有機アミンが堆積する多孔質基板/骨格に対して、40〜60体積%の有機アミン含量であることが示される。これは、以下の計算:
Pcm=骨格材料(例えばシリカまたはアルミナ)の密度(kg/立方メートル)、
PORc=多孔率、すなわち空気流方向に垂直の総表面積に対する開口した壁の面積の比率、
PUR=捕捉された空気に対する放出されたCO2の比率、すなわちCO2の純度、
RH=反応熱、
SH/RH=再生中の顕熱と反応熱RHとの比率、
Savc=骨格の単位体積あたりの表面積(1/表面の平方メートル/立方メートル)、
SH=顕熱、
TA=CO2を飽和するまで含有させるのにかかる時間、すなわち吸着時間、
TS=水蒸気によるストリッピングを使用して再生するのに要する時間、
w=骨格の孔壁の厚さ、
d=平均の孔/チャネルサイズ。
によって決定できる。これらは、このプロセスの設計で考察されるべき重要な設計パラメーターである。このモデルにおいて、計算を簡易化するために、PORcは、総平均面積に対する開いたチャネルの平均面積の比率に等しく、多孔質媒体の壁のチャネルにおける曲線の蛇行性は無視した。したがって、PORc=d2/(d+w)2である。単位体積あたりの表面積は、Savc=4d/(d+w)2=4PORc/dで示される。圧力の低下は、チャネル中の開口部のサイズ、モノリスの空隙率、孔を通る空気流の長さおよび速度によって決まる。
[0052]使用できる基板のタイプの一例は、セルコール.RTM(CELCOR.RTM)という商標名でコーニング(Corning)により製造されたシリカ製モノリスである。このモノリスは、本発明の原理に従って、吸着剤構造用の支持体として使用できる。CO2を含む空気が基板を介して流れるときに高い表面積および低い圧力低下をもたらす多孔性セラミック基板である1つまたはそれより多くのセルコール.RTM.の内部に、吸着剤(例えば第一アミンなど)が担持される(例えばコーティングされるか、または別の方式でそこに固定される)。吸着剤モノリス構造は、例えば、同時係属中の出願に関して説明されている、レンガのように積み重ねられているか、または単一の一体型基板の複数のセルコール.RTM.多孔性セラミック基板を含んでいてもよい。他の例としては、出願公開US2011/0179948で開示された基板および吸着剤、または、Choiらによる報文(Amine-Tethered Solid Adsorbents Coupling High Adsorption Capacity and Regenerability for CO 2 Capture From Ambient Air、Sunho Choiら、CHEMSUSCHEM 2011、4、628〜635、2011、Wiley-VCH Verlag GmbH & Co. KGaA、Weinheim)で説明されているような基板および吸着剤が挙げられる。
=4Ns PORc/Av d Pcm(1−PORc)
この式をPORcについて解くと、下記となる。
[0057]上記構造によって吸着させたCO2の含有量を最大にすることが望ましいために、ポリアミン吸着剤は、所望の高いNsをもたらす。どのような場合においても、多孔質支持体中の孔/チャネル間にできる限り薄い壁を有することが好ましいことが上記の分析から明らかである。孔径をより大きくすることによって多孔率が増加すると、多孔質支持体の密度(Pcm)の減少によって一次的に相殺されることから、含有量(モル/kg)は、孔のサイズとは独立してSavcの減少と一次的な関係である。
wおよびdはナノメートルで示され、L=1.33(Nsn/w(1+w/2d)モル/kg(骨格構造)であることがわかる。Nsn=5部位/立方ナノメートル、およびw=2ナノメートルの場合、約0.5の多孔率によって、400mm2/グラムの表面積、または160,000mm2、およびL=2.5モル/kg(骨格構造)が得られる。
Ld/a=L(0.044)(Pcm(1−PORc))Savm Wc Lm
[式中、支持体の壁の厚さ:We、モノリスの(空気流方向の)長さ:Lm]。
Ld/a=(Ns Savc/Av Pcm(1−PORc))×(0.044)(Pcm(1−PORc))×Savm×We×Lm;
Ld/a=Ns(0.044)/Av)(Save×Savm×We×Lm)
であり、Savcを置換すると、下記のようになる。
[0060]一例において、コーニング製の230セルを有するセルコールモノリスを使用する場合、孔の流れ方向の長さLmは0.146メートルであり、モノリスの単位体積あたりの表面積Savmは約2000m2/m3であり、モノリスの孔壁の厚さWmは0.265mmであり、kg/m2(空気注入部の面積)で示されるCO2量は、Ld/a=L(0.044kg/モル)(Pc Savm 0.146Wm)から決定される。一般的な設計基準は、圧力低下の制約を受ける、すなわち風の力および/またはファンのアレイによって制限されるLおよびLd/aをできるだけ大きくすることであり、これは、230セルを有するコーニング製モノリスのSavm、および0.146mの空気流方向の孔長さ、および2.5m/秒の投入空気流速度に関するモデリング結果を使用する本発明の第一の実施態様で満たされている。
[0074]このプロセスのさらなる改善として、相当量の資本およびエネルギーの節約は、ユニットそれぞれの性能を最適化するために吸着/再生ユニットの隣接するモジュールを統合することによって達成できることが発見された。
(目的1) 劣化を防ぐために、現行の実施態様、すなわち菫青石のモノリスを、空気に晒す前に70℃未満に冷却すること。将来的な吸着剤は、温度をそれほど下げなくてもいいように、より酸素耐性になっている可能性があることに留意すべきであるが、モノリスの温度が低ければ低いほどCO2吸着もより速くなる。
(目的2) プロセスでは可能な限り少ない熱を使用すること。
(目的3) 高純度のCO2を収集すること。
(ボックス3051/モノリスアレイ3041) モノリスアレイは、密封された再生ボックス3051中にあり、水蒸気の再生およびCO2収集をちょうど完了させたところであり;この時点での水蒸気除去圧力は約0.7〜1.0BarAである。これは、残存するあらゆるCO2を押し出すために、ブレークスルー後に多少の余分な水蒸気を導入することを包含していてもよい(以下参照)。
(ボックス3052/モノリスアレイ3042) CO2を捕獲した後、密封された再生ボックス3052にちょうど降下される。ボックス3052の圧力がポンプで0.2〜0.1barに下げられると、それぞれ60℃および45℃になり、これはその圧力での水蒸気の飽和温度である。この空気排出は、当然ながら、空気の量は周囲空気の20〜10%でしかないために、CO2生成物の純度への大きな助けとなると予想され、さらに、電気を使用して1つのボックスの空気をポンプでくみ出すコストは、100パスカルの圧力低下で空気を移動させるのにかかるコストの10%の未満であり、現行の実施態様ではわずか5%でしかない。
T収集およびT添加は独立して調節できるため、この条件は容易に満たすことができる。T添加を最大にするために、T冷却およびT収集を最小化してTエレベーターを低くすることが要求される。気化器およびタンデム式の設計の場合、2つの隣接するモジュールはそれぞれ2つのモジュールアレイを有し、デューティサイクルの損失がないように各々からの2つのフロントボックスと2つのバックボックスとが連結される(それらは互いに半分のサイクル分ずれていると予想される)。空気のみの場合、非タンデム式の設計が有用であり、この場合、T添加がT収集の10倍となる可能性があり、原則的には10のユニットを同期させることができ、ここでユニットnは、1/2の顕熱をユニットn+1に提供すると予想される。また原則的にはN10からの熱を再度N1に戻すこともできるが、これは、追加で5%の熱効率の増加にしかならず、多大な追加コストおよび複雑さを伴うと予想される。
[0094]現行のシステムで稼働させるために、640の個別のモノリスの熱いモノリスアレイから22Kgの水/水蒸気を蒸発させて、例えばモノリスアレイ3042などのアレイを110℃から55℃に冷却し、さらに、10秒以内に蒸発させた水蒸気を、冷たい例えばモノリスアレイ3041で凝縮させて、そのアレイを予熱することが必要である。この温度範囲における水蒸気の潜熱は2.3×106ジュールであるため、T=10秒でHR=50.6×106ジュールを除去する必要がある。
2003 CO2捕獲ゾーン
2006 CO2ストリッピング/再生チャンバー
2008 排気管
2012 貯蔵容器
2014 コンプレッサー
2019 水蒸気コジェネレーター
2023 空気排出ポンプ
3009 セパレーター
3012 供給パイプ、ライン
3014 ライン、バルブ、連結部
3021、3022 ライン
3041、3042 モノリスアレイ
3050〜3053 再生ボックス
Claims (18)
- 二酸化炭素含有空気から濃縮された二酸化炭素を除去し捕獲する方法であって、
第一の二酸化炭素を含む周囲空気流を、50体積%以下の流出ガスと混合し(ここで流出ガスは、炭化水素の燃焼による煙道ガスから発生したものである)、混合された第一の周囲空気流を、第一の二酸化炭素除去構造に向かわせること;ここで二酸化炭素除去構造は、多孔質基板上に支持された、第一の混合された周囲空気混合物から予め決められた量の二酸化炭素が除去されるように発熱を伴い且つ解放可能に二酸化炭素と結合できる吸着剤を含み;
第一の二酸化炭素除去構造を、第一の密封された二酸化炭素捕獲チャンバーに送り、第一の密封された捕獲チャンバーから空気を排気してその中の空気圧を低下させ、水蒸気を120℃以下の温度で第一の二酸化炭素除去構造に送ることにより、吸着剤から二酸化炭素をストリッピングして吸着剤を再生し、濃縮された二酸化炭素が捕獲されるように第一の密封された捕獲チャンバーからストリッピングされた二酸化炭素を除去すること;
第二の二酸化炭素を含む周囲空気流を50体積%以下の流出ガスと混合し(ここで流出ガスは、炭化水素の燃焼による煙道ガスから発生したものである)、混合された周囲空気流を第二の二酸化炭素除去構造に向かわせること;ここで第二の二酸化炭素除去構造は、多孔質基板上に支持された、第二の混合された周囲空気混合物から予め決められた量の二酸化炭素が除去されるように解放可能に二酸化炭素と結合できる吸着剤を含み;
第二の二酸化炭素除去構造を、第二の密封された二酸化炭素捕獲チャンバーに送り、第二の密封された捕獲チャンバーから空気を排気してその中の空気圧を低下させ、水蒸気を120℃以下の温度で第二の二酸化炭素除去構造に送ることにより、吸着剤から二酸化炭素をストリッピングして水蒸気を凝縮させながら吸着剤を再生し、濃縮された二酸化炭素が捕獲されるように第二の密封された捕獲チャンバーからストリッピングされた二酸化炭素を除去すること;
第一の二酸化炭素除去構造が再生サイクルを完了させたときに第二の二酸化炭素除去構造がその再生を実行するように準備されたら、第一の二酸化炭素捕獲チャンバー中の残存する水蒸気を減圧された第二の二酸化炭素捕獲チャンバーに流し込むことにより、飽和水蒸気で再生させる前に第一の二酸化炭素除去構造を冷却し且つ第二の二酸化炭素除去構造を予熱し;第一の二酸化炭素除去構造を第一の捕獲チャンバーから除去して、混合された周囲空気流に移動させるように、第一の二酸化炭素除去構造と第二の二酸化炭素除去構造とをタンデム式で稼働させること;
飽和水蒸気を第二の二酸化炭素捕獲チャンバーに送り、第二の二酸化炭素除去構造を再生し、第二の二酸化炭素除去構造から二酸化炭素および凝縮した水蒸気を除去すること;および
混合された空気流から二酸化炭素を吸収させた後に第一の二酸化炭素除去構造を第一の二酸化炭素捕獲チャンバーに戻し、第一の二酸化炭素捕獲チャンバー中の圧力を低下させて、第二の二酸化炭素捕獲チャンバー中のより高い圧力に向かって圧力を解放させるように、タンデム式の稼働を繰り返すこと;
を含む、上記方法。 - それぞれの捕獲構造から除去された二酸化炭素と凝縮した水蒸気とを分離容器に送り、凝縮した水蒸気を液体として除去し、濃縮された二酸化炭素をさらなる処理に送る、請求項1に記載の方法。
- 残存する水蒸気を除去して少なくとも95%純度の高度に濃縮されたCO2を得るのに十分な程度に圧縮することによって、さらに二酸化炭素を処理する、請求項2に記載の方法。
- それぞれの前記二酸化炭素捕獲チャンバー中の圧力を0.2BarAに以下に低下させる、請求項1に記載の方法。
- それぞれの前記二酸化炭素捕獲チャンバー中の圧力を0.15BarA以下に低下させる、請求項1に記載の方法。
- 前記混合された周囲空気が、周囲空気中のCO2濃度よりも少なくとも2桁大きいCO2濃度を有する、請求項1に記載の方法。
- 前記二酸化炭素除去構造が、シリカ、アルミナ、およびアルミナでコーティングしたシリカからなる群より選択される材料で形成された多孔質基板モノリスのアレイを含み、ここで基板はアミン吸着剤を支持している、請求項1に記載の方法。
- 前記吸着剤が、第一アミンである、請求項7に記載の方法。
- 前記水蒸気が、飽和水蒸気である、請求項1に記載の方法。
- 前記飽和水蒸気が、プロセス熱による水蒸気である、請求項9に記載の方法。
- それぞれの前記二酸化炭素捕獲チャンバー中の圧力を0.1BarAに低下させる、請求項5に記載の方法。
- 再生された前記二酸化炭素除去構造が捕獲チャンバーから除去されるときに、凝縮した水蒸気が基板の孔中に残り、混合された周囲空気流に戻されることにより、混合された空気からCO2を吸収するときの吸着剤および基板の温度が適正化される、請求項1に記載の方法。
- 前記周囲空気が、50体積%未満の流出ガスと混合される、請求項12に記載の方法。
- 二酸化炭素含有空気から二酸化炭素を除去するシステムであって、
一対の二酸化炭素除去構造、ここで各構造は、二酸化炭素を吸収するかまたは二酸化炭素と結合することにより空気から二酸化炭素を除去することが可能な吸着剤、および表面上に吸着剤が支持された多孔質の固体基板、および基板のための可動式の構造支持体を含み;ここで構造支持体は、空気からCO2が除去されるように二酸化炭素含有空気流に晒される位置に吸着剤を支持している;
一対の密封可能なCO2捕獲チャンバー(これらはそれぞれ、CO2を含有する除去構造から二酸化炭素を捕獲するための各二酸化炭素除去構造;二酸化炭素捕獲チャンバーと、除去構造が入った後に密封された二酸化炭素捕獲チャンバー内の大気圧を低下させるための排気ポンプとの間の開閉可能な流体連結手段;二酸化炭素捕獲チャンバーとプロセス熱による水蒸気源との間の開閉可能な流体連結手段;2つの二酸化炭素捕獲チャンバー間の開閉可能な流体連結手段;および各二酸化炭素捕獲チャンバーとCO2収集チャンバーとの間の開閉可能な流体連結手段に対応する);ならびに
二酸化炭素捕獲チャンバーに、および二酸化炭素捕獲チャンバーから二酸化炭素除去構造を移動させるための装置;
を含む、上記システム。 - 前記多孔質固体は、空気から二酸化炭素を吸収するかまたは二酸化炭素と結合する二酸化炭素吸着剤を支持する、高度に多孔質の一体式セラミック構造を含む、請求項9に記載のシステム。
- 一対の垂直に並べられた炭素捕獲構造を含み、ここで該炭素捕獲構造のそれぞれは、垂直に並べられた炭素捕獲構造の対の一方が、交互に且つ連続して二酸化炭素含有空気の軌道中に存在し、それと同時に垂直に並べられた炭素捕獲構造の対の他方が、プロセス熱で加熱されて、吸着剤からそれまでに吸着していた二酸化炭素を分離させることにより、多孔質支持体で吸着剤を再生する方式で選択的に稼働させることができる、請求項9に記載のシステム。
- 前記垂直に並べられた炭素捕獲構造が、交互に且つ連続して二酸化炭素含有空気の軌道中に配置されて、空気から二酸化炭素を除去し、プロセス熱で加熱されるように露出させることにより、吸着剤から二酸化炭素を分離して吸着剤を再生するように設計されており、そのように稼働することが可能な、請求項11に記載のシステム。
- 交互に且つ連続して二酸化炭素含有空気を炭素捕獲構造に送り、プロセス熱を炭素捕獲構造に送ることにより、吸着剤から二酸化炭素を分離して吸着剤を再生するように設計され適合させた、自動的に稼働するバルブシステムを含む、請求項11に記載のシステム。
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US20130312606A1 (en) | 2013-11-28 |
EP2867600A4 (en) | 2016-01-20 |
US20150209718A1 (en) | 2015-07-30 |
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CA2872627A1 (en) | 2013-11-07 |
PL2867600T3 (pl) | 2019-08-30 |
EP2867600A1 (en) | 2015-05-06 |
US9616378B2 (en) | 2017-04-11 |
US9028592B2 (en) | 2015-05-12 |
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US20170209832A1 (en) | 2017-07-27 |
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US9975087B2 (en) | 2018-05-22 |
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