JP5856079B2 - 合成液体炭化水素の製造方法およびフィッシャー−トロプシュ合成用反応器 - Google Patents
合成液体炭化水素の製造方法およびフィッシャー−トロプシュ合成用反応器 Download PDFInfo
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- JP5856079B2 JP5856079B2 JP2012551118A JP2012551118A JP5856079B2 JP 5856079 B2 JP5856079 B2 JP 5856079B2 JP 2012551118 A JP2012551118 A JP 2012551118A JP 2012551118 A JP2012551118 A JP 2012551118A JP 5856079 B2 JP5856079 B2 JP 5856079B2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
- B01J8/067—Heating or cooling the reactor
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/34—Apparatus, reactors
- C10G2/341—Apparatus, reactors with stationary catalyst bed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
- B01J2208/00212—Plates; Jackets; Cylinders
- B01J2208/00238—Adjusting the heat-exchange profile by adapting catalyst tubes or the distribution thereof, e.g. by using inserts in some of the tubes or adding external fins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/19—Details relating to the geometry of the reactor
- B01J2219/194—Details relating to the geometry of the reactor round
- B01J2219/1941—Details relating to the geometry of the reactor round circular or disk-shaped
- B01J2219/1946—Details relating to the geometry of the reactor round circular or disk-shaped conical
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
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- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
さらには、上部の底部に対する長さ比率は1/1〜3/1が好ましい。
ガス時間空間速度が少なくとも2000 l/時の合成ガスを、触媒が充填された複数のチューブ5へ入口3から供給する。同時に、冷却液(例えば水)を、選択された触媒のフィッシャー−トロプシュ法に最適な温度範囲の下限の温度で入口1からシェル6内に入れる。合成ガスが触媒と接触すると、当該ガスはフィッシャー−トロプシュ反応下で放熱しながら液体炭化水素および水に転化する。発生した熱はチューブの壁を介して除去され、冷却液に移動し、当該冷却液は部分的にスチームに順次、転化されるので、移動した熱は蒸発熱により吸収される。生成物は出口4から出され、使用された冷却液は出口2から出される。
2つの構成部分から構成され、かつ、触媒が充填されている全長6mの円筒状チューブを複数備えたシェルアンドチューブ型反応器に、合成ガスを圧力21barおよびチューブ1本あたりのガス流量4kg/時(ガス時間空間速度3000 l/時と同等である)で供給する。
2.5mmコバルト触媒ペレットをチューブ空間率0.4で充填させて用いる;当該触媒は上記ガス時間空間速度における最適温度範囲が210〜217℃である。水を圧力19.1bar(絶対圧力)にて温度210℃でシェルへ供給する。
底部の直径は50mm、上部の直径は25mmであり、それらの比率は2/1である。
上部の長さは3m、底部の長さは3mであり、それらの比率は1/1である。
底部の入口において、圧力勾配は0.1bar/m未満であり、反応温度は210℃から217℃に上昇する。
反応器からの出口において、転化率は80%である;反応器の長さに沿った全部の圧力差は1.5barである。本実施例において、反応器の長さに沿った圧力勾配の挙動についての比較グラフを図4に示す。
全ての実施例において、触媒が充填されたチューブの全長は6mであり、合成ガスは圧力21barおよびチューブ1本あたりの流量4kg/時にて入口で供給する。
2.5mmコバルト触媒ペレットをチューブ空間率0.4で充填させて用いる;当該触媒は上記ガス時間空間速度における最適温度範囲が210〜217℃である。水を圧力19.1bar(絶対圧力)にて温度210℃でシェルへ供給する。
**触媒温度が最適温度をかなり超えて上昇し、その結果、触媒は焼結し、失活する。
Claims (5)
- 以下の工程を含むことにより合成液体炭化水素を製造する方法:
(a)シェルおよび該シェル内にある複数の垂直式チューブを含むチューブ型反応器中、フィッシャー−トロプシュ反応により合成ガスを触媒により転化させる工程であって、冷却液を、前記シェルの底部に供給することができ、かつ前記シェルの上部から出すことができるように、前記反応器が構成されており、チューブ出口におけるチューブ直径の、チューブ入口におけるチューブ直径に対する比率が1.5/1〜2.5/1であり、前記複数のチューブにおける上部の長さの、前記複数のチューブにおける底部の長さに対する比率が1/1〜3/1である、工程;
(b)合成ガスの60〜80%が液体炭化水素に転化すると、前記チューブ型反応器におけるチューブの底部での圧力勾配を0.1bar/m未満まで低下させる工程;および
(c)前記方法の残りの間、前記チューブ型反応器におけるチューブの底部での圧力勾配を0.1bar/m未満に維持する工程。 - (a)シェル、
(b)チューブ入口およびチューブ出口をそれぞれに有する複数のチューブであって、該チューブが触媒を含み、かつ前記シェル内にあるチューブ、
(c)合成ガス入口、
(d)前記シェルの底部に入れるための冷却液入口、
(e)生成物出口、および
(f)前記シェルの上部から出すための冷却液出口を有し、
合成ガスからの液体炭化水素のフィッシャー−トロプシュ合成用反応器であって、
合成ガスからの液体炭化水素の合成の間、合成ガスの60〜80%が液体炭化水素に転化すると、前記チューブ型反応器におけるチューブの底部での圧力勾配が0.1bar/m未満まで低下するように、前記複数のチューブは、底部の断面直径が上部と比較して大きく、前記チューブ出口におけるチューブ直径の、前記チューブ入口におけるチューブ直径に対する比率が1.5/1〜2.5/1であり、前記複数のチューブにおける上部の長さの、前記複数のチューブにおける底部の長さに対する比率が1/1〜3/1である、反応器。 - 前記複数のチューブが円筒形状を有する、請求項2に記載の反応器。
- 前記複数のチューブが2つの構成部分から構成されている、請求項2に記載の反応器。
- 前記複数のチューブが円筒形状を有し、2つの構成部分から構成されている、請求項2に記載の反応器。
Applications Claiming Priority (3)
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RU2010103081 | 2010-02-01 | ||
RU2010103081/04A RU2440400C2 (ru) | 2010-02-01 | 2010-02-01 | Способ получения синтетических жидких углеводородов и реактор для проведения синтеза фишера-тропша |
PCT/RU2011/000054 WO2011093749A2 (en) | 2010-02-01 | 2011-01-31 | Process for producing synthetic liquid hydrocarbons and reactor for fischer-tropsch synthesis |
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JP2013518934A JP2013518934A (ja) | 2013-05-23 |
JP5856079B2 true JP5856079B2 (ja) | 2016-02-09 |
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JP2012551118A Expired - Fee Related JP5856079B2 (ja) | 2010-02-01 | 2011-01-31 | 合成液体炭化水素の製造方法およびフィッシャー−トロプシュ合成用反応器 |
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US (1) | US8524787B2 (ja) |
EP (1) | EP2539420B1 (ja) |
JP (1) | JP5856079B2 (ja) |
CN (1) | CN102741379B (ja) |
AU (1) | AU2011210031B2 (ja) |
CA (1) | CA2787119C (ja) |
RU (1) | RU2440400C2 (ja) |
WO (1) | WO2011093749A2 (ja) |
ZA (1) | ZA201205259B (ja) |
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WO2012083636A1 (zh) * | 2010-12-21 | 2012-06-28 | 北京化工大学 | 利用超重力反应器进行费托合成的方法 |
US9440903B2 (en) * | 2012-09-24 | 2016-09-13 | Arkema Inc. | Shell and tube oxidation reactor with improved resistance to fouling |
US9358526B2 (en) | 2013-11-19 | 2016-06-07 | Emerging Fuels Technology, Inc. | Optimized fischer-tropsch catalyst |
US9180436B1 (en) | 2013-11-19 | 2015-11-10 | Emerging Fuels Technology, Inc. | Optimized fischer-tropsch catalyst |
RU2588617C1 (ru) * | 2015-03-11 | 2016-07-10 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Казанский национальный исследовательский технический университет им. А.Н. Туполева-КАИ" (КНИТУ-КАИ) | Способ проведения экзотермических и эндотермических каталитических процессов частичного превращения углеводородов и реакторная группа для его осуществления |
CN106566574A (zh) * | 2015-10-13 | 2017-04-19 | 亚申科技研发中心(上海)有限公司 | 一种利用焦炉气和转炉气生产费托化学品的方法 |
US10737236B2 (en) | 2015-11-23 | 2020-08-11 | Sabic Global Technologies B.V. | Structural catalyst with internal heat transfer system for exothermic and endothermic reactions |
KR102003429B1 (ko) * | 2016-10-19 | 2019-07-24 | 주식회사 포스코건설 | 합성석유 제조장치 및 제조방법 |
ES2909139T3 (es) * | 2016-12-09 | 2022-05-05 | Velocys Tech Limited | Proceso para el manejo de un reactor tubular altamente productivo |
CN108607475A (zh) * | 2018-04-28 | 2018-10-02 | 上海奕玛化工科技有限公司 | 一种草酸二甲酯加氢制乙二醇用反应器 |
CN109589874B (zh) * | 2018-11-19 | 2021-08-24 | 江苏玖鸿化工技术有限公司 | 一种银法甲醛装置中的甲醇氧化器 |
CN109603687B (zh) * | 2018-11-19 | 2021-08-24 | 江苏玖鸿化工技术有限公司 | 一种高效率的银法甲醛装置中的甲醇氧化器 |
US11841172B2 (en) | 2022-02-28 | 2023-12-12 | EnhancedGEO Holdings, LLC | Geothermal power from superhot geothermal fluid and magma reservoirs |
US12055131B2 (en) | 2022-02-28 | 2024-08-06 | EnhancedGEO Holdings, LLC | Geothermal power from superhot geothermal fluid and magma reservoirs |
US11905797B2 (en) | 2022-05-01 | 2024-02-20 | EnhancedGEO Holdings, LLC | Wellbore for extracting heat from magma bodies |
US11918967B1 (en) | 2022-09-09 | 2024-03-05 | EnhancedGEO Holdings, LLC | System and method for magma-driven thermochemical processes |
US11913679B1 (en) | 2023-03-02 | 2024-02-27 | EnhancedGEO Holdings, LLC | Geothermal systems and methods with an underground magma chamber |
US11912573B1 (en) | 2023-03-03 | 2024-02-27 | EnhancedGEO Holdings, LLC | Molten-salt mediated thermochemical reactions using geothermal energy |
US11897828B1 (en) | 2023-03-03 | 2024-02-13 | EnhancedGEO, Holdings, LLC | Thermochemical reactions using geothermal energy |
US11912572B1 (en) | 2023-03-03 | 2024-02-27 | EnhancedGEO Holdings, LLC | Thermochemical reactions using geothermal energy |
US12060765B1 (en) | 2023-07-27 | 2024-08-13 | EnhancedGEO Holdings, LLC | Float shoe for a magma wellbore |
US11905814B1 (en) | 2023-09-27 | 2024-02-20 | EnhancedGEO Holdings, LLC | Detecting entry into and drilling through a magma/rock transition zone |
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US2404816A (en) | 1945-01-08 | 1946-07-30 | Thompson Prod Inc | Seal surface |
DE2929300A1 (de) * | 1979-07-19 | 1981-01-29 | Linde Ag | Reaktor zur durchfuehrung katalytischer endothermer oder exothermer reaktionen |
DE3247821A1 (de) * | 1982-12-23 | 1984-09-27 | Kernforschungsanlage Jülich GmbH, 5170 Jülich | Reaktionsrohr fuer eine exotherme, heterogen katalysierte gasreaktion, insbesondere zur fuehrung einer methanisierungsreaktion |
US7316804B2 (en) * | 2001-08-02 | 2008-01-08 | Ineos Usa Llc | Flow reactors for chemical conversions with heterogeneous catalysts |
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- 2011-01-31 CN CN201180005855.8A patent/CN102741379B/zh not_active Expired - Fee Related
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CA2787119C (en) | 2014-10-07 |
CA2787119A1 (en) | 2011-08-04 |
RU2010103081A (ru) | 2011-08-10 |
US8524787B2 (en) | 2013-09-03 |
ZA201205259B (en) | 2013-03-27 |
EP2539420B1 (en) | 2017-09-06 |
EP2539420A2 (en) | 2013-01-02 |
WO2011093749A3 (en) | 2011-12-29 |
CN102741379A (zh) | 2012-10-17 |
CN102741379B (zh) | 2014-12-17 |
AU2011210031B2 (en) | 2016-04-28 |
AU2011210031A1 (en) | 2012-08-30 |
RU2440400C2 (ru) | 2012-01-20 |
JP2013518934A (ja) | 2013-05-23 |
US20120322898A1 (en) | 2012-12-20 |
WO2011093749A2 (en) | 2011-08-04 |
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