JP6460979B2 - 生物起源の活性炭ならびにそれを作製および使用する方法 - Google Patents
生物起源の活性炭ならびにそれを作製および使用する方法 Download PDFInfo
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- JP6460979B2 JP6460979B2 JP2015511634A JP2015511634A JP6460979B2 JP 6460979 B2 JP6460979 B2 JP 6460979B2 JP 2015511634 A JP2015511634 A JP 2015511634A JP 2015511634 A JP2015511634 A JP 2015511634A JP 6460979 B2 JP6460979 B2 JP 6460979B2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 1357
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- 238000000034 method Methods 0.000 title claims description 306
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- 239000000203 mixture Substances 0.000 claims description 177
- 229910021389 graphene Inorganic materials 0.000 claims description 148
- 239000000654 additive Substances 0.000 claims description 141
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 137
- 239000002028 Biomass Substances 0.000 claims description 124
- 238000006243 chemical reaction Methods 0.000 claims description 103
- 229910052760 oxygen Inorganic materials 0.000 claims description 89
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 87
- 239000001301 oxygen Substances 0.000 claims description 87
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 86
- 239000011261 inert gas Substances 0.000 claims description 72
- 229910052757 nitrogen Inorganic materials 0.000 claims description 68
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 47
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 12
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 12
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- 239000004115 Sodium Silicate Substances 0.000 claims description 11
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- 239000012286 potassium permanganate Substances 0.000 claims description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- 150000002497 iodine compounds Chemical class 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
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- QGZKDVFQNNGYKY-AKLPVKDBSA-N Ammonia-N17 Chemical compound [17NH3] QGZKDVFQNNGYKY-AKLPVKDBSA-N 0.000 claims 1
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Description
本国際特許出願は、2012年5月7日出願の米国仮特許出願第61/643,741号、2012年11月2日出願の米国仮特許出願第61/721,827号、および2012年12月14日出願の米国仮特許出願第61/737,514号の優先権の利益を主張するものであり、これらはそれぞれ、参照によりその全体が本明細書に組み込まれる。
いくつかの実施形態において、図10を参照して、生物起源の活性炭を生成するためのプロセスは、以下のステップを含む:
(a)バイオマスを含む出発炭素含有供給原料を提供することと、
(b)前述の供給原料を任意に乾燥させて、前述の供給原料から水分の少なくとも一部を除去することと、
(c)1つ以上の間接的に加熱された反応帯域において、前述の供給原料を機械的に運搬し、前述の供給原料を、実質的に不活性のガスを含む蒸気流および水または二酸化炭素のうちの少なくとも一方を含む活性化剤と向流的に接触させて、固体、凝縮性蒸気、および非凝縮性ガスを発生させることと(前述の凝縮性蒸気および前述の非凝縮性ガスは前述の蒸気流に入る)、
(d)前述の反応帯域から前述の蒸気流の少なくとも一部を除去して、分離された蒸気流を発生させることと、
(e)前述の分離された蒸気流またはその熱的に処理された形態の少なくとも一部を、ステップ(c)の前に前述の供給原料に、かつ/または前述の反応帯域(複数可)のガス入口に再循環させることと、
(f)生物起源の活性炭として前述の反応帯域(複数可)から前述の固体の少なくとも一部を回収することとを含む。
この実施例は、添加物、すなわち、臭化鉄(II)を有する生物起源の活性炭生成物の生成を実証する。
・370℃4帯域熱
・300℃で動作する高温窒素導入システム
・0.4立方フィート/分のガス抽出プローブ流量
・低酸素環境
・30分間の生成物処理時間
実施例1に従って調製された臭化鉄(II)で前処理した生成物の試料の寸法を減少させ、水銀捕獲実験で利用した。
ガス合成混合物(窒素と、24.7ppmの一酸化炭素、24.9ppmの一酸化窒素、および25.1ppmの二酸化硫黄;Linde Gas North America)を用いて、実施例1に従って1%の過マンガン酸カリウム水溶液で前処理した生物起源の活性炭の吸着特性を評価した。MKSモデル2030フーリエ変換赤外線(FTIR)検出器を用いて、CO、NO、およびSO2の濃度をリアルタイムで測定した。
ガスの合成混合物(窒素と、8.52%の二酸化炭素および11.00%の酸素;Linde Gas North America)を用いて、実施例1に従って1%の過マンガン酸カリウム水溶液で前処理した生物起源の活性炭の吸着特性を評価した。
木材基板の赤松大チップ、ダグラスファー円筒(直径1.25インチの断片)、およびダグラスファー断片(約2インチ×2インチ)を、任意に加熱された窒素ガス流を有する装填ホッパーに装填した。任意に、添加物の1%水溶液(例えば、NaOHおよび/もしくはKOH)を、ホッパーにある間にスプレーで、または添加物水溶液中にバイオマスを浸して木材基板に塗布した。塗布方法にかかわらず、バイオマスが乾燥する前にこの添加物水溶液をバイオマスに30分間浸透させた。反応器が所望の温度に到達した時点で、反応器の回転を開始し、材料供給システムを作動させて木材基板を緩徐に供給した。それぞれのバッチの反応器の加熱された部分における平均滞留時間が表3に示される。反応器の加熱された部分を出た後、熱分解材料は、放出ホッパーに収集された。コンベヤは、さらなる分析のために放出ホッパーから生物起源の活性炭生成物を除去した。
この実施例は、高熱価を有する生物起源の活性炭生成物の生成を実証する。
この実施例は、高熱価を有する生物起源の活性炭生成物の生成を実証する。
生物起源の活性炭を、実施例6の一般方法に従って製粉されたキルン乾燥木ダボ接合によって実質的に調製した。
およそ1インチ×1/2インチ×1/8インチに寸法決定された赤松木材チップを、実施例6の一般方法に従って、600℃および30分間の滞留時間で熱分解した。結果として生じる生物起源の活性炭生成物を「試料A」と称する。
生物起源の活性炭生成物中の固定炭素レベルへの滞留時間の影響を、1つの供給原料バッチをほぼ等しい粒径を有する供給原料の断片からなる4つのほぼ等しい質量のグループに分けることによって調査した。4つのグループをそれぞれ、実施例6の一般方法に従って、350℃で、それぞれ、0分間、30分間、60分間、および120分間の滞留時間で熱分解に供した。それぞれの試料の固定炭素含有量をASTM D3172によって決定した。結果が表11および対応する図18に示される。
生物起源の活性炭生成物中の固定炭素レベルへの熱分解温度の影響を、1つの供給原料バッチをほぼ等しい粒径を有する供給原料の断片からなる5つのほぼ等しい質量のグループに分けることによって調査した。5つのグループをそれぞれ、実施例6の一般方法に従って、30分間の滞留時間で熱分解に供した。それぞれの試料の固定炭素含有量をASTM D3172によって決定した。結果が表12および対応する図19に示される。
生物起源の活性炭生成物中の固定炭素レベルへの供給原料の粒径の影響を、3つの赤松バイオマスのグループ:おがくず(平均粒径約0.0625インチ)、チップ(平均粒径約1インチ×1/2インチ×1/8インチ)、および大きい塊(1−1/8インチの直径および約1.5インチの長さを有する円筒)を熱分解することによって調査した。3つのグループをそれぞれ、実施例6の一般方法に従って、400℃で30分間熱分解に供した。それぞれの試料の固定炭素含有量をASTM D3172によって決定した。結果が表13および対応する図20に示される。
この実施例は、生物起源の活性炭生成物の質量収率への酸素レベルの影響を実証する。
炭素回収ユニット(「CRU」)の使用による固定炭素含有量および熱価の増加を実証する。
この実施例は、バイオマス処理ユニットへの加熱窒素ガスの導入の影響を実証する。
この実施例は、添加物、すなわち、臭化鉄(II)を有する生物起源の活性炭生成物の生成を実証する。
この実施例は、その後の活性化ステップの前に事前炭化した基板上にガス相炭素質種を再捕獲する肯定的な利点を実証する。
Claims (46)
- 生物起源の活性炭を生成するための連続方法であって、
(a)バイオマスを含む出発炭素含有供給原料を提供することと、
(b)前記供給原料を乾燥させて、前記供給原料から水分の少なくとも一部を除去することと、
(c)1つ以上の間接的に加熱された反応帯域において、前記供給原料を機械的に運搬し、前記供給原料を、不活性のガスを含む蒸気流および水または二酸化炭素のうちの少なくとも1つを含む活性化剤と向流的に接触させて、固体、凝縮性蒸気、および非凝縮性ガスを発生させることと、
(d)前記反応帯域から前記蒸気流の少なくとも一部を除去して、分離された蒸気流を発生させることと、
(e)前記分離された蒸気流またはその熱的に処理された形態の少なくとも一部を、ステップ(c)の前に前記供給原料に、および/または前記反応帯域のガス入口に再循環させることと、
(f)生物起源の活性炭として前記反応帯域から前記固体の少なくとも一部を回収することと、を含む、前記連続方法。 - ステップ(c)の前に、前記供給原料が12重量%以下の量の水分を含有する、請求項1に記載の方法。
- ステップ(c)の前に、前記供給原料が6重量%以下の量の水分を含有する、請求項2に記載の方法。
- ステップ(c)の前に、前記供給原料が2重量%以下の量の水分を含有する、請求項3に記載の方法。
- 前記供給原料にさらに水は添加されず、前記活性化剤が水を含み、前記活性化剤に含まれる前記水が元来前記供給原料に含まれる水分に由来する、請求項1に記載の方法。
- 前記活性化剤が水および二酸化炭素の両方を含む、請求項1に記載の方法。
- 前記水と前記二酸化炭素の比率が前記固体の活性化を増加させるように最適化される、請求項6に記載の方法。
- 前記間接的に加熱された反応帯域のうちの1つの最低限が、最低700℃から最高900℃から選択される反応温度で維持される、請求項1に記載の方法。
- 前記間接的に加熱された反応帯域のすべてが950℃以下の最高反応温度で維持される、請求項1に記載の方法。
- ステップ(d)が、前記反応帯域から前記凝縮性蒸気の少なくとも一部を除去することを含む、請求項1に記載の方法。
- ステップ(d)が、前記反応帯域から前記蒸気流のすべてを除去することを含む、請求項10に記載の方法。
- 前記分離された蒸気流の少なくとも一部が、ステップ(c)の前に前記供給原料に、および/または前記反応帯域の前記ガス入口に再循環させる前に、熱的に処理される、請求項1に記載の方法。
- 前記分離された蒸気流またはその熱的に処理された形態が、合計1重量%以下の量の一酸化炭素およびVOC含有量を含む、請求項1に記載の方法。
- ステップ(e)が、前記分離された蒸気流またはその熱的に処理された形態をさらに加熱することをさらに含む、請求項1に記載の方法。
- ステップ(e)が、水、二酸化炭素、窒素、および酸素からなる群から選択される1つ以上の種を導入することによって、前記分離された蒸気流またはその熱的に処理された形態のガス組成を調整することをさらに含む、請求項1に記載の方法。
- ステップ(e)後、前記分離された蒸気流が、最小0%から最大100%の水、最小0%から最大100%の二酸化炭素、最小0%から最大100%の窒素、および最小0%から最大100%の酸素を含む、請求項15に記載の方法。
- ステップ(e)後、前記分離された蒸気流が、最大16%、最大14%、最大12%、最大10%、最大8%以下、最大6%、最大4%、または最大2%の酸素及び最小0%の酸素を含む、請求項15に記載の方法。
- ステップ(e)後、前記分離された蒸気流が、最小5%、最小10%、最小15%、最小20%、最小25%、最小30%、最小35%、最小40%、最小45%、最小50%、最小55%、最小60%、最小65%、最小70%、最小75%、最小80%、最小85%、最小90%、最小95%、または100%の二酸化炭素及び最大100%の二酸化炭素を含む、請求項15または請求項16に記載の方法。
- ステップ(e)後、前記分離された蒸気流が、最小5%、最小10%、最小15%、最小20%、最小25%、最小30%、最小35%、最小40%、最小45%、最小50%、最小55%、最小60%、最小65%、最小70%、最小75%、最小80%、最小85%、最小90%、最小95%、または100%の酸素及び最大100%の酸素を含む、請求項15または請求項16に記載の方法。
- ステップ(e)後、前記分離された蒸気流が、最小70重量%の窒素、最小75%の窒素、最小80%の窒素、最小85%の窒素、最小90%の窒素、最小95%の窒素、または100%の窒素及び最大100%の窒素を含む、請求項15または請求項16に記載の方法。
- 前記分離された蒸気流またはその熱的に処理された形態の少なくとも一部が、前記1つ以上の間接的に加熱された反応帯域のうちの第1の反応帯域に前記供給原料を機械的に供給するように構成された送達システムに導入される、請求項1に記載の方法。
- 前記活性化剤の少なくとも一部が、前記分離された蒸気流またはその熱的に処理された形態に由来する、請求項1に記載の方法。
- 請求項1に記載の方法によって生成された生物起源の活性炭の炭素含有量が、ステップ(e)以外のステップ(a)、(b)、(c)、(d)、および(f)を含む方法によって生成された生物起源の活性炭の炭素含有量を超える、請求項1に記載の方法。
- 請求項1に記載の方法によって生成された生物起源の活性炭の表面積が、ステップ(e)以外のステップ(a)、(b)、(c)、(d)、および(f)を含む方法によって生成された生物起源の活性炭の表面積を超える、請求項1に記載の方法。
- 請求項1に記載の方法によって生成された生物起源の活性炭のヨウ素価(Iodine Number)が、ステップ(e)以外のステップ(a)、(b)、(c)、(d)、および(f)を含む方法によって生成された生物起源の活性炭のヨウ素価を超える、請求項1に記載の方法。
- 請求項2に記載の方法によって生成された生物起源の活性炭のグラフェンの量が、ステップ(e)以外のステップ(a)、(b)、(c)、(d)、および(f)を含む方法によって生成された生物起源の活性炭のグラフェンの量を超える、請求項2に記載の方法。
- ステップ(f)が、生物起源の活性炭として前記反応帯域から前記固体のすべてを回収することを含む、請求項1に記載の方法。
- 添加物が、ステップ(a)〜(f)のうちの1つ以上の前、最中、または後に導入され、前記添加物が、酸、塩基、塩、金属、金属酸化物、金属水酸化物、金属ハロゲン化物、ヨウ素、ヨウ素化合物、またはこれらの組み合わせからなる群から選択される、請求項1に記載の方法。
- 添加物が、ステップ(a)〜(f)のうちの1つ以上の前、最中、または後に導入され、前記添加物がマグネシウム、マンガン、アルミニウム、ニッケル、鉄、クロム、ケイ素、ホウ素、セリウム、モリブデン、リン、タングステン、バナジウム、塩化鉄、臭化鉄、酸化マグネシウム、ドロマイト、ドロマイト石灰、フルオライト、フルオロスパー、ベントナイト、酸化カルシウム、石灰、水酸化ナトリウム、水酸化カリウム、臭化水素、塩化水素、ケイ酸ナトリウム、過マンガン酸カリウム、有機酸、ヨウ素、ヨウ素化合物、およびこれらの組み合わせからなる群から選択される、請求項1に記載の方法。
- 前記生物起源の活性炭が、少なくとも500、少なくとも1000、少なくとも1500、少なくとも2000、または少なくとも2000から最大2250のヨウ素価を特徴とする、請求項1に記載の方法。
- 前記生物起源の活性炭が、少なくとも1000m2/g、少なくとも1500m2/g、または少なくとも2000m2/gの表面積を特徴とする、請求項1に記載の方法。
- 前記生物起源の活性炭がグラフェンを含む、請求項1に記載の方法。
- 前記生物起源の活性炭が外部から印加された磁場に応答する、請求項1に記載の方法。
- 前記生物起源の活性炭の電気伝導度が、前記出発炭素含有供給原料の電気伝導度を超える、請求項1に記載の方法。
- 前記生物起源の活性炭の電気容量が、前記出発炭素含有供給原料の電気容量を超える、請求項1に記載の方法。
- 二次元または三次元で基板上にグラフェンを成長させるために、反応器に前記分離された蒸気流またはその熱的に処理された形態の少なくとも一部を導入することをさらに含む、請求項1に記載の方法。
- 生物起源の活性炭を生成するための連続方法であって、、
(a)バイオマスを含む出発炭素含有供給原料を提供することと、
(b)前記供給原料を乾燥させて、前記供給原料から水分の少なくとも一部を除去することと、
(c)1つ以上の間接的に加熱された反応帯域において、前記供給原料を機械的に運搬し、前記供給原料を、不活性のガスを含む蒸気流および水または二酸化炭素のうちの少なくとも1つを含む活性化剤と向流的に接触させて、固体、凝縮性蒸気、および非凝縮性ガスを発生させることと、
(d)前記反応帯域から前記蒸気流の少なくとも一部を除去して、分離された蒸気流を発生させることと、
(e)外部源からの炭素含有液体または蒸気流を、ステップ(c)の前に前記供給原料に、および/または前記反応帯域のガス入口に導入することと、
(f)生物起源の活性炭として前記反応帯域から前記固体の少なくとも一部を回収することと、を含む、前記連続方法。 - グラフェン含有の生物起源の活性炭を生成するための連続方法であって、
(a)バイオマスを含む出発炭素含有供給原料を提供することと、
(b)前記供給原料を乾燥させて、前記供給原料から水分の少なくとも一部を除去することと、
(c)1つ以上の間接的に加熱された反応帯域において、前記供給原料を機械的に運搬し、前記供給原料を、不活性のガスを含む蒸気流および水または二酸化炭素のうちの少なくとも1つを含む活性化剤と向流的に接触させて、固体、凝縮性蒸気、および非凝縮性ガスを発生させることと、
(d)前記反応帯域から前記蒸気流の少なくとも一部を除去して、分離された蒸気流を発生させることと、
(e)前記分離された蒸気流またはその熱的に処理された形態の少なくとも一部を、ステップ(c)の前に前記供給原料に、および/または前記反応帯域のガス入口に再循環させることと、
(f)前記反応帯域から前記固体の少なくとも一部を回収することであって、前記固体がグラフェン含有の生物起源の活性炭を含む前記回収することと、
を含む、前記連続方法。 - 前記グラフェン含有の生物起源の活性炭の少なくとも一部からグラフェンを分離することをさらに含む、請求項38に記載の方法。
- 前記分離が、機械的分離、磁気分離、および/または電気的分離を含む、請求項39に記載の方法。
- (g)前記固体を処理して前記固体中のグラフェン含有量を増加させることをさらに含む、請求項38に記載の方法。
- (g’)前記固体の少なくとも一部を用いて基板またはデバイス上にグラフェンを製作することをさらに含む、請求項38に記載の方法。
- 前記グラフェン含有の生物起源の活性炭が、外部から印加された磁場に応答する、請求項38に記載の方法。
- 前記グラフェン含有の生物起源の活性炭の電気伝導度が、前記炭素含有供給原料の電気伝導度を超える、請求項38に記載の方法。
- 前記グラフェン含有の生物起源の活性炭の電気容量が、前記炭素含有供給原料の電気容量を超える、請求項38に記載の方法。
- グラフェン含有の生物起源の活性炭を生成するための連続方法であって、
(a)バイオマスを含む出発炭素含有供給原料を提供することと、
(b)前記供給原料を乾燥させて、前記供給原料から水分の少なくとも一部を除去することと、
(c)1つ以上の間接的に加熱された反応帯域において、前記供給原料を機械的に運搬し、前記供給原料を、不活性のガスを含む蒸気流および水または二酸化炭素のうちの少なくとも1つを含む活性化剤と向流的に接触させて、固体、凝縮性蒸気、および非凝縮性ガスを発生させることと、
(d)前記反応帯域から前記蒸気流の少なくとも一部を除去して、分離された蒸気流を発生させることと、
(e)前記分離された蒸気流またはその熱的に処理された形態の少なくとも一部を、ステップ(c)の前に前記供給原料に、および/または前記反応帯域のガス入口に再循環させて、前記固体中の炭素の表面積を増加させることと、
(f)生物起源の活性炭として前記反応帯域から前記固体の少なくとも一部を回収することと、を含み、
前記生物起源の活性炭が、乾燥ベースで、55重量%以上の全炭素、15重量%以下の水素、および1重量%以下の窒素を含み、
前記生物起源の活性炭の少なくとも一部が、グラフェンの形態で存在し、
前記生物起源の活性炭組成物が、500よりも高いヨウ素価を特徴とし、
前記生物起源の活性炭が、外部から印加された磁場に応答する、前記連続方法。
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