JP5847811B2 - バイオマスからメタンを製造する方法 - Google Patents
バイオマスからメタンを製造する方法 Download PDFInfo
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- JP5847811B2 JP5847811B2 JP2013515318A JP2013515318A JP5847811B2 JP 5847811 B2 JP5847811 B2 JP 5847811B2 JP 2013515318 A JP2013515318 A JP 2013515318A JP 2013515318 A JP2013515318 A JP 2013515318A JP 5847811 B2 JP5847811 B2 JP 5847811B2
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- Prior art keywords
- reformer
- hydroconversion
- hydropyrolysis
- methane
- steam
- 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.)
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 116
- 239000002028 Biomass Substances 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000000034 method Methods 0.000 claims description 73
- 239000003054 catalyst Substances 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 21
- 238000000197 pyrolysis Methods 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910003294 NiMo Inorganic materials 0.000 claims description 10
- 239000003463 adsorbent Substances 0.000 claims description 9
- 238000006392 deoxygenation reaction Methods 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000008246 gaseous mixture Substances 0.000 claims description 7
- 239000002241 glass-ceramic Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 229910001570 bauxite Inorganic materials 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical group C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 5
- 238000002485 combustion reaction Methods 0.000 claims 3
- 239000012530 fluid Substances 0.000 claims 2
- 239000006096 absorbing agent Substances 0.000 claims 1
- 230000003635 deoxygenating effect Effects 0.000 claims 1
- 238000005243 fluidization Methods 0.000 claims 1
- 239000006112 glass ceramic composition Substances 0.000 claims 1
- 230000005285 magnetism related processes and functions Effects 0.000 claims 1
- 238000002407 reforming Methods 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000002309 gasification Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 238000005367 electrostatic precipitation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000011044 inertial separation Methods 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 241001474374 Blennius Species 0.000 description 1
- -1 H 2 S Chemical compound 0.000 description 1
- 244000207740 Lemna minor Species 0.000 description 1
- 235000006439 Lemna minor Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 235000001855 Portulaca oleracea Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010907 stover Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Description
本発明は、バイオマスを直接メタンに熱化学的に変換する統合された方法に関する。ここで使用する用語「バイオマス」は、生きているか、または死んだ生物体に由来する生物学的材料を意味し、リグノセルロース系材料、例えば木材、水生材料、例えば藻類、水生植物、海藻、及び動物副生物及び排出物、例えば食用にならない部分、脂肪及び下水スラッジ、を包含する、一態様では、本発明は、バイオマスからメタンを製造するための、多段階水素化熱分解製法に関する。
Claims (26)
- バイオマスからメタンを製造する方法であって、
a)分子状水素及び脱酸素触媒を含む水素化熱分解反応容器中で、バイオマスを水素化熱分解し、チャー及び蒸気を含んでなる水素化熱分解生成物を製造する工程、
b)前記水素化熱分解生成物から前記チャーを分離し、チャーが減少した水素化熱分解生成物を製造する工程、
c)水素化転化触媒を使用する水素化転化反応容器中で、前記チャーが減少した水素化熱分解生成物を水素化転化し、水素化転化生成物を製造する工程、
d)前記水素化転化生成物から、結露水とCO2、H2、及びメタンを含んでなり、チャーを含まない気体状混合物を分離する工程、
e)少なくとも前記気体状混合物の第一部分を、原料として、スチームリホーマー中に導入し、その中で、前記メタンが改質され、リホーマーCO2及びリホーマーH2を製造する工程、および
f)少なくとも前記気体状混合物の第二部分を、メタン化容器に導入し、追加のメタンを形成する工程を含んでなり、
水素化熱分解工程a)および水素化転化工程c)がともに発熱性の工程である方法。 - 前記結露水が前記スチームリホーマー中に導入され、前記メタンを改質する、請求項1に記載の方法。
- 外部の供給源から水を前記スチームリホーマー中に導入し、前記メタンを改質する、請求項2に記載の方法。
- 前記スチームリホーマーに導入される原料の第一部分を燃焼装置に導入し、燃焼させ、それによって、スチームと共に前記スチームリホーマーへ導入される原料の第二部分を加熱し、前記リホーマーCO2及び前記リホーマーH2を形成する、請求項1に記載の方法。
- 前記水素化熱分解生成物から分離された前記チャーの一部をファーネス中で燃焼し、それによって、前記スチームリホーマー中に水と共に前記スチームリホーマーへ導入される原料を加熱し、前記リホーマーCO2及び前記リホーマーH2を形成する、請求項1に記載の方法。
- 前記チャーの一部を、スチームボイラーの燃焼室で燃焼し、スチームを形成し、前記スチームを前記スチームリホーマー中に、前記原料と共に導入する、請求項1に記載の方法。
- 前記リホーマーH2の少なくとも一部を、メタン化容器に導入し、追加のメタンを形成する、請求項1に記載の方法。
- 前記リホーマーH2の少なくとも一部が、前記水素化熱分解反応容器に循環され、前記バイオマスの前記水素化熱分解に使用される、請求項1に記載の方法。
- 前記脱酸素触媒及び前記水素化転化触媒の少なくとも一方がガラス−セラミック材料である、請求項1に記載の方法。
- 前記水素化熱分解が、0.2〜10gmバイオマス/gm触媒/hrの範囲内の毎時重量空間速度で行われる、請求項1に記載の方法。
- 前記水素化転化が、0.2〜3gmバイオマス/gm触媒/hrの範囲内の毎時重量空間速度で行われる、請求項1に記載の方法。
- 前記水素化熱分解反応容器が、流動床を含む流動床反応器である、請求項1に記載の方法。
- 前記水素化熱分解反応容器中のガス滞留時間が1分間未満である、請求項12に記載の方法。
- 前記チャーが前記流動床反応器から、実質的に前記流動床の上からだけ除去される、請求項12に記載の方法。
- 前記水素化熱分解反応容器が、流動床を含む流動床反応器であり、前記チャーが、前記流動床反応器から、慣性、静電気、及び磁気プロセスの少なくとも一つを使用するエネルギー的チャー分離により除去される、請求項1に記載の方法。
- 前記脱酸素触媒が、硫黄化CoMo、硫黄化NiMo、触媒活性のガラス−セラミック、ボーキサイト、及びそれらの混合物及び組合せからなる群から選択される、請求項1に記載の方法。
- 混合物または単一の選択された吸着剤の注入により予備加熱されたホットガスフィルターが、水素化熱分解反応容器及び水素化転化反応容器の一方を出るガスから、選択された不純物を除去するのに使用される、請求項1に記載の方法。
- 前記メタン反応用器に導入されるリホーマーH2の一部が、圧力スイング吸着(PSA)を用いて、前記リホーマーCO2より分離されたH2である、請求項7に記載の方法。
- 前記水素化転化生成物のガスにおいて水−ガス−シフト反応を行う工程をさらに含んでなる、請求項1に記載の方法。
- a)脱酸素触媒の存在下、流動床水素化熱分解反応容器中で、バイオマスを水素化熱分解し、流動化のために水素含有ガスを使用し、水素化熱分解生成物を製造する工程、
b)水素化転化触媒および水素の存在下、水素化転化反応容器中において、水素化熱分解生成物を水素化転化し、水素化転化生成物を製造する工程、
c)前記水素化転化生成物から、結露水とCO2、H2、及びメタンを含んでなる気体状混合物を分離する工程、および
d)前記気体状混合物の少なくとも第一部分が、メタンハイドレート回収プロセスに導入され、純粋なメタン流および前記水素化熱分解反応容器に循環される水素を製造する工程を含んでなり、
水素化熱分解工程a)および水素化転化工程b)がともに発熱性の工程である、水素化熱分解プロセス。 - 少なくとも前記気体状混合物の第二部分を、原料として、スチームリホーマーに導入し、リホーマーCO2及びリホーマーH2を製造する工程をさらに含む、請求項20に記載のプロセス。
- 前記結露水を、前記スチームリホーマーに導入し、前記メタンを改質する、請求項21に記載のプロセス。
- 前記スチームリホーマーに導入される原料の第一部分を、燃焼装置に導入し、燃焼させ、それによって、スチームと共に前記スチームリホーマーへ導入される原料の第二部分を加熱し、前記リホーマーCO2及び前記リホーマーH2を形成する、請求項21に記載のプロセス。
- 前記バイオマスの前記水素化熱分解のために、前記リホーマーH2の少なくとも一部が、前記水素化熱分解反応容器に循環される、請求項21に記載のプロセス。
- 混合物または単一の選択された吸着剤の注入により、予備加熱された高温ガスフィルターを使用し、水素化熱分解反応容器および水素化転化反応容器の一方に存在する特定の不純物を除去する、請求項20に記載のプロセス。
- 前記水素化転化生成物のガスにおいて水−ガス−シフト反応を行う工程をさらに含んでなる、請求項20に記載の方法。
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US12/815,743 US8915981B2 (en) | 2009-04-07 | 2010-06-15 | Method for producing methane from biomass |
US12/815,743 | 2010-06-15 | ||
PCT/US2011/001048 WO2011159334A1 (en) | 2010-06-15 | 2011-06-09 | Method for producing methane from biomass |
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JP2013528688A (ja) | 2013-07-11 |
MX2012014604A (es) | 2013-05-06 |
CN110066669A (zh) | 2019-07-30 |
EP2582778B1 (en) | 2023-06-07 |
CA2802321C (en) | 2017-01-31 |
UA112523C2 (uk) | 2016-09-26 |
WO2011159334A1 (en) | 2011-12-22 |
AU2011265763A1 (en) | 2013-01-10 |
EP2582778C0 (en) | 2023-06-07 |
BR112012032043B1 (pt) | 2019-10-22 |
CN104593024A (zh) | 2015-05-06 |
BR112012032043A2 (pt) | 2016-11-08 |
CA2802321A1 (en) | 2011-12-22 |
AU2011265763B2 (en) | 2016-07-14 |
EP2582778A4 (en) | 2014-04-30 |
RU2012157780A (ru) | 2014-07-20 |
EP2582778A1 (en) | 2013-04-24 |
NZ604743A (en) | 2014-12-24 |
ECSP13012389A (es) | 2015-02-28 |
US8915981B2 (en) | 2014-12-23 |
PE20131059A1 (es) | 2013-09-23 |
US20100251615A1 (en) | 2010-10-07 |
MY160418A (en) | 2017-03-15 |
RU2573567C2 (ru) | 2016-01-20 |
MX341104B (es) | 2016-08-08 |
CL2012003531A1 (es) | 2013-06-07 |
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